CN103503582B - The one-piece type flexible printing substrate of stiffening plate - Google Patents

Abstract

Present invention offer is a kind of sequentially to include stiffening plate, thermosetting binding agent, dielectric film, the one-piece type flexible printing substrate of stiffening plate of the film of subsidiary Wiring pattern as the one-piece type FPC of stiffening plate, and the dielectric film in its structure at least contains binder polymer and spherical organic pearl, therefore the thermosetting binding agent of stiffening plate and the adhesion of dielectric film are superior, and warpage is small.

Description

The one-piece type flexible printing substrate of stiffening plate

Technical field

The present invention relates to a kind of one-piece type flexible printing substrate of stiffening plate, it is characterised in that the thermosetting of stiffening plate is bonded Agent and the adhesion that dielectric film is directly pressed are superior, and warpage is small.

Background technology

In recent years, it is soft in the electronic equipments such as the mobile phone, video camera, notebook computer that miniaturization, lightweight are developed rapidly Flexible printing substrate soft and with pliability（Hereinafter referred to as FPC（Flexible Printed Circuit board））Become It is indispensable.On the other hand, FPC is that thickness is tens of μm to hundreds of μm and the distributing board with high bendability, so need to be to it In carry out reinforcement with the position of the part phase attaching such as connector, to ensure required installation strength.Therefore, generally the zero of FPC Stiffening plate is adhesively fixed via thermosetting binding agent in the back side of part installation region, to seek local intensity to improve（For example With reference to patent document 1~3）.

[prior art literature]

Patent document 1：Japanese Patent Application Laid " JP 2010-114185 ", on May 20th, 2010 public affairs Open.

Patent document 2：Japanese Patent Application Laid " JP 2010-6921 ", on January 14th, 2010 is open.

Patent document 3：Japanese Patent Application Laid " JP 2011-61070 ", on March 24th, 2011 is open.

The content of the invention

[the problem to be solved in the present invention]

Patent document 1 is conceived to sufficient heat resistance（Scolding tin heat resistance）Stiffening plate, and can be compared with there is provided one kind The circuit connecting section or the stiffening plate of installation portion being used in flexible printing substrate well.In addition, patent document 2 is conceived to thermmohardening Property binding agent, and there is provided a kind of with superior storage stability, caking property, the binding agent group of scolding tin heat resistance and processability Compound and bonding sheet.But, though stiffening plate and thermosetting binding agent is constitute the one-piece type FPC of stiffening plate key element, but if Stiffening plate and thermosetting binding agent each single characteristic are only improved, the spy needed for the one-piece type FPC of stiffening plate can not be still met Property.If for example, not improving FPC and thermosetting binding agent adhesion, can not be shown as the one-piece type FPC of stiffening plate Good characteristic.

In addition, patent document 3 is conceived to FPC outermost layer i.e. cover layer, and there is provided one kind by cover layer It is upper to set ditch portion to expand the bond area of the binding agent to bond FPC and stiffening plate, so as to improve scratching for adhesion strength Property printing distributing board.But, it is used as the method that ditch portion is set on cover layer, it is proposed that blasting treatment, embossed, plasma-based Processing etc., and this this may result in manufacturing cost and further increases.

Therefore, the inventors of the present invention are conceived to FPC outermost layer i.e. dielectric film, for the thermosetting with stiffening plate The flexibility and warpage of the one-piece type FPC of adhesion and stiffening plate between binding agent has carried out making great efforts research.

[technical scheme for solving problem]

The inventors of the present invention have carried out making great efforts research to solve described problem, and outcome research has gone out with following The one-piece type flexible printing substrate of stiffening plate of feature：Sequentially include（A）Stiffening plate,（B）Thermosetting binding agent,（C）Dielectric film, （D）The film of subsidiary Wiring pattern, should（C）Dielectric film at least contains（a）Binder polymer,（b）Spherical organic pearl.And learn In the one-piece type flexible printing substrate of the stiffening plate, the adhesion between the thermosetting binding agent and dielectric film of stiffening plate is very excellent More.Based on these discoveries, the present invention is completed.It is one-piece type by possessing the stiffening plate of following innovative techniques scheme in the present invention Flexible printing substrate, the problem of can solve the problem that above-mentioned.

That is, the present invention is a kind of one-piece type flexible printing substrate of stiffening plate, and it sequentially includes stiffening plate（A）, thermosetting Binding agent（B）, dielectric film（C）, subsidiary Wiring pattern film（D）, it is characterised in that：The dielectric film（C）At least contain adhesive Polymer（a）And spherical organic pearl（b）.

In addition, in the one-piece type flexible printing substrate of stiffening plate of the present invention, preferably described dielectric film（C）Also contain：Containing choosing The particulate of at least one kind of element in the group that free phosphorus, aluminium and magnesium are constituted（c）.

In addition, in the one-piece type flexible printing substrate of stiffening plate of the present invention, it is also preferred that dielectric film（C）It is by containing heat Hardening resin（d）Resin combination obtained.

In addition, in the one-piece type flexible printing substrate of stiffening plate of the present invention, it is also preferred that dielectric film（C）It is by gathering containing light Close initiator（e）Photosensitive polymer combination obtained.

[The effect of invention]

As described above, the present invention is sequentially to include stiffening plate（A）, thermosetting binding agent（B）, dielectric film（C）, incidentally match somebody with somebody The film of line pattern（D）The one-piece type FPC of stiffening plate, and the dielectric film（C）At least contain binder polymer（a）And spherical have Machine pearl（b）.Therefore the present invention plays following effect：Adhesion between the thermosetting binding agent and dielectric film of stiffening plate is excellent More, and warpage is small.

Brief description of the drawings

Fig. 1 is the one-piece type FPC of stiffening plate structure chart.

Fig. 2 is schematic diagram when being measured to the amount of warpage of film.

[description of reference numerals]

1 basilar memebrane

2 Wiring patterns

The film of 3 subsidiary Wiring patterns

4 dielectric films

5 FPC

6 stiffening plates

7 thermosetting binding agents

8 somoothing boards

9 amount of warpage

10 dielectric film laminated chips

Embodiment

Hereinafter, the present invention is described in detail.

The one-piece type FPC of stiffening plate of the present invention, as long as sequentially including（A）Stiffening plate,（B）Thermosetting binding agent,（C）Absolutely Velum,（D）The film of subsidiary Wiring pattern, and should（C）Dielectric film at least contains（a）Binder polymer and（b）Spherical organic pearl .

In the one-piece type FPC of stiffening plate of the present invention, the thermosetting binding agent of stiffening plate and the adhesion of dielectric film are superior, And warpage is small.Speculate that this discovery has benefited from following reason.That is, by importing spherical organic filler into dielectric film, insulation is made There is convex-concave in the surface of film, and thus the bond area expanded between dielectric film and the thermosetting binding agent of stiffening plate, close Connecing property is improved.General technology on improving adhesion, for example, can obtain anchor effect by sloughing filler （anchor effect）, and in contrast to this, without the disengaging of spherical organic pearl with regard to that can put forward adhesion in the present invention Height, therefore will not produce and slough pollution problem caused by filler.In addition, by using spherical organic filler, stress is delayed With, thus destruction toughness be improved so that adhesion can be improved, and then can obtain flexibility, therefore it is small to obtain warpage The one-piece type FPC of stiffening plate.

Hereinafter, to the present invention the one-piece type FPC of stiffening plate,（A）Stiffening plate,（B）Thermosetting binding agent,（C）Dielectric film, （D）The film of subsidiary Wiring pattern is illustrated.

[the one-piece type FPC of stiffening plate]

Fig. 1 is the one-piece type FPC of stiffening plate of present invention structure chart, but the present invention is not limited to the structure of diagram.It is first First, possessing Wiring pattern（2）And basilar memebrane（1）'s（D）The film of subsidiary Wiring pattern（3）On, formed（C）Dielectric film（4）, by This obtains FPC（5）.Then, via（B）Thermosetting binding agent（7）, will（A）Stiffening plate（6）It is formed at（C）Dielectric film（4） On, it thus can obtain the one-piece type FPC of stiffening plate of the present invention.

[（A）Stiffening plate]

In the present invention（A）As long as stiffening plate is not limited then for the material of reinforcement flexible printing substrate.Such as conduct The reinforcement plate material of thicker, can enumerate paper phenol, expoxy glass plate etc..In addition, as slim reinforcement plate material, can enumerate poly- Acid imide film, polyester film, metallic plate（Copper coin, aluminium sheet）Deng.

For the one-piece type FPC of stiffening plate of the present invention, if using polyimide film as stiffening plate, can obtain heat-resisting The superior one-piece type distributing board of stiffening plate of property, flexibility, it is advantageous to.

The thickness of the polyimide film is not particularly limited, such as preferably 75 μm to 225 μm.The polyimide film If thickness is less than 75 μm, then the required supportive of support flexible printing substrate can not be obtained sometimes.On the other hand, if thickness is big In 225 μm, then the integral thickness of the one-piece type flexible printing substrate of stiffening plate can become too much, and drive in the wrong direction in miniaturization, gently The tendency of quantization.

The polyimide film is not particularly limited, for example, can enumerate the trade name of Kaneka Co., Ltd. manufacture Apical75NPI, Apical125NPI, Apical225NPI, Apical75AH, 125AH, 225AH etc..

[（B）Thermosetting binding agent]

In the present invention（B）As long as thermosetting binding agent is general thermosetting binding agent, then can suitably it select, example The thermosetting binding agent of epoxy or propylene can such as be enumerated.On the thermosetting binding agent of epoxy, for example, it can enumerate Trade name D3410, D3411 of Sony Chemical ＆ Information Device Co., Ltd. manufacture etc..In addition, on The thermosetting binding agent of propylene, for example, can enumerate Du Pont（Dupont）The trade name Pyralux LF0100 of company's manufacture, Pyralux FR0100 etc..In addition, as propylene-epoxy thermosetting binding agent, such as Sony Chemical ＆ can be enumerated Trade name D3450, D3451 of Information Device Co., Ltd. manufacture etc..

In the present invention（B）The processing method of thermosetting binding agent is not particularly limited, for example, can enumerate utilizing hot pressing Pressurization and/or heating formation method.Pressurization and/or heating molding condition during hot pressing is not particularly limited.For example can hot pressing temperature 100~ 180 DEG C, 0.5~5.0kgf/cm of hot pressing pressure², hot pressing time heat/pressure shaping is carried out under conditions of 10~90 minutes, by This is processed to thermosetting binding agent.During by the control of pressurization and/or heating molding condition in the scope, stiffening plate and insulation Adhesion can be shown between film, it is advantageous to.

[（C）Dielectric film]

In the present invention（C）Dielectric film is the film of 5~100 μm of the thickness with insulating properties.

The thickness of the dielectric film of the present invention can be measured by any means, for example, can use according to standard in Japanese Industrial Standards JIS K54003.5 method is measured.By by thickness control in the scope, the flexibility of dielectric film, electric insulation Reliability is just superior, it is advantageous to.If below 5 μm of thickness, the electrical insulation reliability of dielectric film will be reduced sometimes, if thickness For more than 100 μm, the flexibility of dielectric film will be reduced sometimes.

In the present invention（C）Dielectric film need at least contain（a）Binder polymer and（b）Spherical organic pearl.By containing （a）Composition and（b）Composition, dielectric film and can be expanded by the bond area between cohesive body, and stress can be relaxed, so that Destruction toughness is improved, and then adhesion is improved, and can also obtain flexibility, therefore can obtain the small stiffening plate one of warpage Build FPC, it is advantageous to.

[（a）Binder polymer]

In the present invention（a）Binder polymer is：It is solubility to organic solvent, and the weight converted with polyethylene glycol is equal Molecular weight is more than 1,000, less than 1,000,000 polymer.

The organic solvent is not particularly limited, for example, can enumerate：The sulfoxide such as dimethyl sulfoxide (DMSO), diethyl sulfoxide system is molten Agent；N,N-dimethylformamide, N, the formyl amine series solvent such as N- diethylformamides；DMAC N,N' dimethyl acetamide, N, N- diethyls The acetyl amine series solvent such as yl acetamide；The pyrrolidones series solvent such as METHYLPYRROLIDONE, NVP； Or hexamethyl phosphoramide, gamma-butyrolacton etc..Also can optionally, by these organic polar solvents and then with dimethylbenzene or toluene etc. Aromatic hydrocarbon is applied in combination.

In more detail, it can such as enumerate：Monoethylene glycol dimethyl ether（1,2- dimethoxy-ethanes）, diethylene glycol dimethyl ether （Double (2- methoxy ethyls) ethers）, TRIGLYME（Double (2- methoxy ethoxies) ethane of 1,2-）, tetraethylene glycol diformazan Ether（Double [2- (2- methoxyethoxyethyls)] ethers）, monoethylene glycol diethyl ether（1,2- diethoxyethane）, diethylene glycol two Ether（Double (2- ethoxyethyl groups) ethers）, dibutyl ethylene glycol ether（Double (2- butoxyethyl groups) ethers）Etc. symmetrical diol bisether class； Methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol methyl ether acetate, ethylene glycol list Butyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters（Alias：Carbitol acetate, acetic acid 2- (2- Butoxyethoxies) second Ester)）, butyl carbitol acetate, acetic acid 3- methoxybutyls, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether second The acetate esters such as acid esters, dipropylene glycol methyl ether acetic acid esters, propylene-glycol diacetate, 1,3 butylene glycol diacetate esters；DPG Methyl ether, tripropylene glycol methyl ether, Propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, three Propylene glycol n-propyl ether, propane diols phenylate, dimethyl ether, 1,3- dioxolane, ethylene glycol monobutyl ether, diethylene glycol The ether solvents such as single ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether.

Organic solvent solubility is the soluble index relative to organic solvent, can be according in the parts by weight of organic solvent 100 Middle dissolving（a）The parts by weight of composition, to determine organic solvent solubility.Dissolved relative to the parts by weight of organic solvent 100 （a）If more than the parts by weight of parts by weight 5 of composition, then can be considered as and have soluble relative to organic solvent.Organic solvent solubility Assay method is not particularly limited, for example, can determine by the following method：Added to the parts by weight of organic solvent 100（a）The weight of composition 5 Measure part, at 40 DEG C stir 1 hour after, be cooled to room temperature and place more than 24 hours, be then confirmed whether it is do not occur it is non-molten Solve the homogeneous solution of thing and precipitate.

In the present invention（a）The weight average molecular weight of composition can be for example measured by following methods.

（Weight average molecular weight is determined）

Use device：The equal device with eastern Cao HLC-8220GPC

Chromatographic column：Eastern Cao TSK gel Super AWM-H（6.0mm I.D.×15cm）× 2

Guard column：Eastern Cao TSK guard column Super AW-H

Eluent：The H of LiBr and 20mM containing 30mM₃PO₄DMF（Dimethylformamide）

Flow velocity：0.6mL/min

Chromatogram column temperature：40℃

Testing conditions：RI（Refractive Index, refractive index）：Polarity（+）, the response time（0.5sec）

Test article concentration：About 5mg/mL

Reference material：PEG（Polyethylene glycol, polyethylene glycol）

By the way that weight average molecular weight control in the scope, is obtained（C）The flexibility of dielectric film, chemical-resistant It is just superior, it is advantageous to.If weight average molecular weight is below 1,000, then（C）The flexibility and chemical-resistant of dielectric film are sometimes Reduction, if weight average molecular weight is more than 1,000,000, then contains（a）Composition and（b）The viscosity of the resin combination of composition is sometimes Rise.

In the present invention（a）Composition is not particularly limited, for example, can enumerate：Poly- urethane based resin, poly- (methyl) propylene It is resin, polyethylene-based resin, polystyrene resin, poly- ethylene system resin, polypropylene-based resin, polyimides system resins, poly- Acid amides system resin, polyacetals system resin, polycarbonate-based resin, polyester based resin, Polyphony Ether resin, polyphenylene sulfide system tree Fat, polyether sulfone system resin, polyether-ether-ketone system resin etc., they can be used alone or two or more is applied in combination.Wherein, if making I.e. poly- urethane based resin of resin for containing urethane bond with poly- (methyl) acrylic resin and intramolecular etc.,（a）Composition is just Can be easily penetrate into（b）The inside of composition, so as to（a）Composition with（b）Interface between composition obtains firm caking property. Then, contain（a）Composition and（b）Obtained by the resin combination of composition is hardened（C）The flexibility of dielectric film, bending resistance are just It is improved, and（C）The warpage of dielectric film is small, it is advantageous to.

Intramolecular in the present invention has the resin containing urethane bond to be：It is solubility to organic solvent, intramolecular has containing extremely The repeat unit of few 1 urethane bond, and the weight average molecular weight converted using polyethylene glycol is 1, more than 000,1, less than 000,000 Polymer.

The resin that intramolecular in the present invention contains urethane bond can be obtained by arbitrarily reacting, such as under can making State formula（1）

HO-R₁-OH

Formula（1）

Shown diol compound（In formula, R₁Represent the organic group of divalent）And following formulas（2）

OCN-X₁-NCO

Formula（2）

Shown diisocyanate cpd（In formula, X₁Represent the organic group of divalent）Reacted, so that under being had State formula（3）

Formula（3）

The shown repeat unit containing urethane bond（In formula, R₁And X₁The organic group of divalent is separately represented, n represents more than 1 Integer）Structure.

As long as the diol compound in the present invention is said structure, it is not particularly limited, for example, can enumerates：Ethylene glycol, Diethylene glycol, propane diols, 1,3 butylene glycol, 1,4- butanediols, 1,5- pentanediols, neopentyl glycol, 3- methyl isophthalic acids, 5- pentanediols, 1,6-HD, 1,8- ethohexadiols, 2- methyl 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols, 1,4- cyclohexanediols, 1, The alkane glycol such as 4- cyclohexanedimethanols；Polyethylene glycol, polypropylene glycol, poly- (1,4- butanediols), 1,4- butanediols and neopentyl glycol The polyoxy alkylene glycol such as random copolymer；The polyester-diol for making polyalcohol and polynary acid reaction and obtaining；With carbonic ester skeleton PCDL；The lactones such as gamma-butyrolacton, 6-caprolactone, δ-valerolactone gather oneself obtained by after opening Interior esterdiol；Bisphenol-A, the ethylene oxide adduct of bisphenol-A, the propylene oxide adduct of bisphenol-A, hydrogenated bisphenol A, A Hydrogenated Bisphenol A A ethylene oxide adduct, propylene oxide adduct of hydrogenated bisphenol A etc..These compounds, which can be used alone or combine, to be made Use two or more.

Polyethylene glycol ought particularly be employed, it is polypropylene glycol, poly- 1,4- butanediols, polyoxy alkylene glycol, polyester-diol, poly- During the long chain diols such as carbonate diol, polycaprolactone glycol, obtained by after resin combination is hardened（C）The springform of dielectric film Amount can be reduced, and bendability, low warpage are advantageous, from these from the aspect of, be preferred.

As long as the diisocyanate cpd in the present invention is said structure, it is not particularly limited, for example, can enumerates：Two Phenylmethane -2,4'- diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6, 3'- dimethyl diphenylmethane -2,4'- diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- Or 6,2'- or 6,3'- diethyl diphenyl methane -2,4'- diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5, 2'- or 5,3'- or 6,2'- or 6,3'- dimethoxydiphenyl methane -2,4'- diisocyanate, diphenyl methane -4,4'- two Isocyanates, diphenyl methane -3,3'- diisocyanate, diphenyl methane -3,4'- diisocyanate, diphenyl ether -4,4'- two Isocyanates, UVNUL MS-40,4'- diisocyanate, diphenyl sulphone (DPS) -4,4'- diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, first Benzene -2,6- diisocyanate, m-xylylene diisocyanate, terephthalylidene diisocyanate, the isocyanides of naphthalene -2,6- two The aromatic diisocyanate compounds such as acid esters, 4,4'- [double (4- Phenoxyphenyls) propane of 2,2-] diisocyanate；Hydrogenation two Methylenebis phenyl isocyanate, hydrogenation XDI, IPDI, the isocyanide of ENB two The alicyclic diisocyanate compound such as acid esters；Hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, bad ammonia Aliphatic diisocyanate compound such as sour diisocyanate etc..These compounds can be used alone or be applied in combination 2 kinds with On.

The synthetic method of resin of the intramolecular containing urethane bond in the present invention can be：According to making hydroxyl number and isocyanic acid The ratio of ester group number reaches the mode of " more than NCO/hydroxyl=0.5 and less than 2.0 ", adjustment diol compound and The allotment amount of diisocyanate cpd, and in the absence of solvent, or make diol compound and isocyanide in organic solvent Ester compound is reacted.

If different with two again after can the diol compound be mixed in addition, diol compound of more than two kinds need to be used Cyanate esters are reacted, or each diol compound can also be made individually to be reacted with diisocyanate cpd. In addition, after diol compound is reacted with diisocyanate cpd, it is isocyanates that can also make the end of acquisition Compound is reacted with other diol compounds again, and it is anti-reaction product is carried out with diisocyanate cpd Should.In addition, during using diisocyanate cpd of more than two kinds, can also use with using feelings during two or more diol compound Condition identical reaction scheme.It so, it is possible that resin of the desired, intramolecular containing urethane bond is made.

The reaction temperature of diol compound and diisocyanate cpd is preferably 40~160 DEG C, more preferably 60~150 ℃.If less than 40 DEG C, the reaction time can long, if it exceeds 160 DEG C, then can occur in course of reaction three-dimension type react and Easily cause gelation.Reaction time can suitably select according to the scale of batch, the reaction condition used.In addition, according to Need, can also be in these catalysis such as the metals such as tertiary amines, alkali metal, alkaline-earth metal, tin, zinc, titanium, cobalt or semi metallic compound Reacted in the presence of agent.

Above-mentioned reaction can also be carried out in the absence of solvent, but in order to control reaction, it is generally desirable in organic solvent Reacted in system.Organic solvent as used herein is not particularly limited, for example, the solvent illustrated above can be used.

The amount of organic solvent used during reaction, is preferably capable of causing the solute weight concentration ie in solution in reaction solution Concentration reaches more than 5 weight %, below 90 weight % amount.Solute weight concentration in reaction solution is with more than 10 weight %, 80 weights Amount below % is preferred.If solution concentration is less than 5%, it is difficult to cause polymerisation and cause reaction speed to decline sometimes, and nothing Method obtains the material with desired structure, so not good enough.

The resin that intramolecular in the present invention contains urethane bond is preferred and then contains：Selected from by (methyl) acryloyl group, carboxylic At least one kind of organic group in the group that base, imide are constituted.(methyl) acryloyl group refers to acryloyl group and/or methyl-prop Enoyl-.Containing (methyl) if the resin combination photosensitive polymer combination of acryloyl group, then photonasty can be improved, So can be so that the ultraviolet of short time irradiates and hardens the photosensitive polymer combination.If in addition, contain carboxyl, resin group Dissolubility of the compound in dilute alkali aqueous solution developer solution can be improved, so fine figure can be formed with the development of short time Case.If in addition, containing imide, obtained by resin combination is hardened（C）The heat resistance of dielectric film and hot and humid Under the conditions of electrical insulation reliability can be improved.

Here, the resin containing urethane bond containing (methyl) acryloyl group and intramolecular, can be obtained by arbitrarily reacting. For example can be on the basis of using diol compound, diisocyanate cpd, also using following formulas（4）

Formula（4）

The compound of shown hydroxyl and at least one (methyl) acryloyl group（In formula, R₂Represent the organic of m+1 valencys Base, R₃Hydrogen or alkyl is represented, m represents 1~3 integer）And/or following formulas（5）

Formula（5）

The shown compound containing NCO and at least one (methyl) acryloyl group（In formula, X₂Represent l+1 valencys Organic group, X₃Hydrogen or alkyl is represented, l represents 1~3 integer）To be reacted, so as to be contained (methyl) acryloyl group and be divided Son includes the resin of urethane bond.

In the present invention, hydroxyl and at least one (methyl) are as long as the compound of acryloyl group is said structure, then without spy Do not limit, for example, can enumerate：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, 2- hydroxyl -1- acryloxy -3- methacryloxypropyls Base propane, o-phenyl phenol glycidol ether (methyl) acrylate, polyethyleneglycol (methyl) acrylate, pentaerythrite three (methyl) acrylate, isocyanuric acid two (methyl) acrylic acid three (2- hydroxyethyls) ester, 1,4- cyclohexanedimethanols list (methyl) Acrylate, (methyl) acrylic acid 4- hydroxylphenyl esters, (methyl) acrylic acid 2- (4- hydroxy phenyls) ethyl ester, N- methylol acryloyls Amine, 3,5- dimethyl -4- hydroxybenzyl acrylamides etc..These compounds, which may be used alone or in combination, uses two or more.

In the present invention, containing NCO and at least one (methyl) as long as the compound of acryloyl group is said structure, then It is not particularly limited, for example, can enumerates：Isocyanic acid 2- (methyl) acryloyloxyethyl ester, isocyanic acid 1,1- (double acryloxies Methyl) ethyl ester, isocyanic acid 2- (2- methacroyloxyethoxies) ethyl ester etc..These compounds, which may be used alone or in combination, to be made Use two or more.

In addition, containing carboxyl and intramolecular the resin containing urethane bond, can be obtained by arbitrarily reacting.It can such as use On the basis of diol compound, diisocyanate cpd, also using following formulas（6）

Formula（6）

The shown compound containing 2 hydroxyls and 1 carboxyl（In formula, R₄Represent the organic group of trivalent）To be reacted, from And obtain containing the resin of carboxyl and intramolecular containing urethane bond.

In the present invention, as long as the compound containing 2 hydroxyls and 1 carboxyl is said structure, it is not particularly limited, for example It can enumerate：Double (methylol) propionic acid of 2,2-, double (2- hydroxyethyls) propionic acid of 2,2-, 2,2- double (3- hydroxypropyls) propionic acid, 2,3- Double (methylol) butyric acid of dihydroxy -2 Methylpropionic acid, 2,2-, double (2- hydroxyethyls) butyric acid of 2,2-, double (the 3- hydroxyls third of 2,2- Base) butyric acid, 2,3- dihydroxy butyric acid, 2,4- dihydroxy -3,3- acid dimethyls, 2,3- ustilic acid As, 2,3- dihydroxies Yl benzoic acid, 2,4- dihydroxy-benzoic acids, 2,5- dihydroxy-benzoic acids, 2,6- dihydroxy-benzoic acids, 3,4- dihydroxy-benzoic acids, 3,5- dihydroxy-benzoic acids etc..These compounds, which may be used alone or in combination, uses two or more.

Especially when employing the compound containing 2 hydroxyls and 1 carboxyl of fatty family, photosensitive polymer combination Photonasty is just superior, sees from the side, is preferred.

In addition, containing imide and intramolecular the resin containing urethane bond, can be obtained by arbitrarily reacting.For example may be used With on the basis of using diol compound, diisocyanate cpd, also using following formulas（7）

Formula（7）

Shown tetracarboxylic dianhydride（In formula, Y represents the organic group of 4 valencys）To be reacted, so as to obtain containing imide And resin of the intramolecular containing urethane bond.

In the present invention, as long as tetracarboxylic dianhydride is said structure, it is not particularly limited, for example, can enumerates：3,3',4, 4'- benzophenone tetracarboxylic dianhydride (BTDA)s, pyromellitic acid anhydride, 3,3', the double O-phthalic acid dianhydrides of 4,4'- oxygen, 2,2- it is double [4- (3, 4- di carboxyl phenyloxies) phenyl] propane dianhydride, double (4- hydroxy phenyls) propane benzhydryl ester -3,3', the 4,4'- tetracarboxylic acids of 2,2- Dianhydride, 3,3', 4,4'- diphenyl sulfone tetraformic acids dianhydride, 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 2,3,3', 4- bibenzene tetracarboxylics Tetracarboxylic dianhydrides such as dianhydride, 5- (2,5- dioxotetrahydro -3- furyls) -3- methyl -3- cyclohexene -1,2- dicarboxylic acid anhydrides etc.. These compounds can be used alone or two or more is applied in combination.

Poly- (methyl) propylene resin in the present invention refers to：It is solubility relative to organic solvent, and containing making (first Base) acrylic acid and/or (methyl) acrylate derivative carry out repeat unit obtained by copolymerization, and the weight converted with polyethylene glycol Average molecular weight is more than 1,000, less than 1,000,000 polymer.

Poly- (methyl) propylene resin in the present invention can be obtained by arbitrarily reacting, for example can in a solvent and (methyl) acrylic acid and/or (methyl) acrylate derivative in the presence of radical polymerization initiator, is set to be reacted to obtain .

(methyl) acrylate derivative in the present invention is not particularly limited, for example, can enumerate：(methyl) acrylic acid first Ester, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid nonyl ester, (first Base) decyl acrylate, (methyl) dodecylacrylate, (methyl) stearyl acrylate ester, (methyl) benzyl acrylate etc., this A little compounds, which may be used alone or in combination, uses two or more.Among these (methyl) acrylate derivatives, with regard to resin combination The flexibility of dielectric film and the viewpoint of chemical-resistant for, particularly preferably use (methyl) methyl acrylate, (methyl) third Olefin(e) acid ethyl ester, (methyl) butyl acrylate.

On above-mentioned radical polymerization initiator, for example, it can enumerate：Azobis isobutyronitrile, azo double (2- methylbutyronitriles), The Azos such as 2,2' azobis 2,4 dimethyl valeronitrile；T-butyl hydroperoxide, cumene hydroperoxide, peroxidating The organic peroxides such as benzoyl, cumyl peroxide, di-t-butyl peroxide；Potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate Deng persulfate；Hydrogen peroxide etc..These compounds can be used alone or two or more is applied in combination.

The consumption of the radical polymerization initiator is relative to the used parts by weight of monomer 100, preferably 0.001~5 Parts by weight, more preferably 0.01~1 parts by weight.If less than 0.001 parts by weight, being just difficult to be reacted sometimes, if more than 5 weight Part, the molecular weight of poly- (methyl) propylene resin will decline sometimes.

The solvent load during reaction can preferably make it that the solute weight concentration ie in solution concentration in reaction solution reaches 5 More than weight %, 90 below weight %, more preferably more than 20 weight %, below 70 weight %.If solution concentration is less than 5 weight %, have When can be difficult to cause polymerisation and cause reaction speed to decline, and the material with desired structure can not be obtained.If in addition, molten Liquid concentration is higher than 90 weight %, then reaction solution turns into high viscosity sometimes and causes reaction uneven.

The temperature of the reaction is preferably 20~120 DEG C, more preferably 50~100 DEG C.If temperature is less than 20 DEG C, react Time can be long, if more than 120 DEG C, may occur intense reaction or side reaction and occur three-dimensional cross-linked, cause gelation. Reaction time can according to the scale of batch, using reaction condition suitably select.

In the present invention（a）Composition is if polyimides system resins, then（C）The heat resistance of dielectric film is improved, so It is preferred that.The polyimides system resins refer to：Intramolecular has the repeat unit of the imide containing at least one, and with poly- second two The polymer that the weight average molecular weight of alcohol conversion is more than 1,000, less than 1,000,000.

Polyimides system resins in the present invention can be obtained by arbitrarily reacting, for example, can make the formula（7）Institute The tetracarboxylic dianhydride shown is reacted to obtain with diamino compounds.

Diamino compounds in the present invention are not particularly limited, for example, can enumerate：M-phenylene diamine (MPD), o-phenylenediamine, to benzene Diamines, an aminobenzyl amine, PAB amine, double (3- aminophenyls) thioethers, (3- aminophenyls) (4- aminophenyls) sulphur Ether, double (4- aminophenyls) thioethers, double (3- aminophenyls) sulfoxides, (3- aminophenyls) (4- aminophenyls) sulfoxide, double (4- ammonia Base phenyl) sulfoxide, double (3- aminophenyls) sulfones, (3- aminophenyls) (4- aminophenyls) sulfone, double (4- aminophenyls) sulfones, 3, 4'- diaminourea benzophenone, 4,4'- diaminourea benzophenone, 3,3'- diaminourea benzophenone, 3,3'- diaminodiphenyl-methanes, 3, 4'- diaminodiphenyl-methanes, 4,4'- diaminodiphenyl-methanes, 4,4'- diaminodiphenyl ethers, 3,3'- diaminourea hexichol Ether, 3,4'- diaminodiphenyl ethers, double [4- (3- amino-benzene oxygens) phenyl] sulfoxides, double [4- (amino-benzene oxygen) phenyl] sulfoxides, (4- aminophenoxy phenyls) (3- aminophenoxy phenyls) phenyl] it is sulfoxide, double [4- (3- amino-benzene oxygens) phenyl] sulfones, double [4- (4- amino-benzene oxygens) phenyl] sulfone, (4- aminophenoxy phenyls) (3- aminophenoxy phenyls) benzene sulfone, double [4- (3- ammonia Phenoxyl) phenyl] thioether, double [4- (amino-benzene oxygen) phenyl] thioethers, (4- aminophenoxy phenyls) (3- amino-benzene oxygens Phenyl) aralkyl sulfid, 3,3'- diaminourea N- benzanilides, 3,4'- diaminourea N- benzanilides, 4,4'- diaminourea N- benzene Formailide, double [4- (3- amino-benzene oxygens) phenyl] methane, double [4- (4- amino-benzene oxygens) phenyl] methane, [4- (4- amino Phenoxyphenyl)] [4- (3- aminophenoxy phenyls)] methane, 1,1- double [4- (3- amino-benzene oxygens) phenyl] ethane, 1,1- Double [4- (4- amino-benzene oxygens) phenyl] ethane, 1,1- [4- (4- aminophenoxy phenyls)] [4- (3- aminophenoxy phenyls)] Double [4- (3- amino-benzene oxygens) phenyl] ethane of ethane, 1,2-, 1,2- double [4- (4- amino-benzene oxygens) phenyl] ethane, 1,2- [4- (4- aminophenoxy phenyls)] [4- (3- aminophenoxy phenyls)] ethane, 2,2- are double [4- (3- amino-benzene oxygens) phenyl] Propane, 2,2- double [4- (4- amino-benzene oxygens) phenyl] propane, 2,2- [4- (4- aminophenoxy phenyls)] [4- (3- aminobenzenes Phenyl)] propane, double [3- (3- amino-benzene oxygens) the phenyl] -1,1,1,3,3,3- HFC-236fas of 2,2-, the double [4- (4- of 2,2- Amino-benzene oxygen) phenyl] -1,1,1,3,3,3- HFC-236fas, 2,2- [4- (4- aminophenoxy phenyls)] [4- (3- aminobenzenes Phenyl)] -1,1,1,3,3,3- HFC-236fas, double (3- amino-benzene oxygens) benzene of 1,3-, 1,4- are double (3- amino-benzene oxygens) Double (4- amino-benzene oxygens) benzene of benzene, 1,4-, double (4- amino-benzene oxygens) benzene of 1,3-, 4,4'- double (4- amino-benzene oxygens) biphenyl, 4, 4'- double (3- amino-benzene oxygens) biphenyl, double [4- (3- amino-benzene oxygens) phenyl] ketone, double [4- (4- amino-benzene oxygens) phenyl] Ketone, double [4- (3- amino-benzene oxygens) phenyl] ethers, double [4- (4- amino-benzene oxygens) phenyl] ethers, poly- 1,4- butanediols are double (to ammonia Yl benzoic acid) ester, double (PABA) esters of poly- (tetramethylene/3- methyl tetramethyleneethers) glycol, the double 4- of trimethylene The double PABA esters of Aminobenzoate, TOPOT 2,2′ p phenylenebis PABA ester, metaphenylene, the double 4- amino of bisphenol-A Benzoic ether, 2,4- diaminobenzoic acids, 2,5- diaminobenzoic acids, 3,5- diaminobenzoic acids, 3,3'- diaminourea -4,4'- Dicarboxylate biphenyl, 4,4'- diaminourea -3,3'- dicarboxylate biphenyls, 4,4'- diaminourea -2,2'- dicarboxylate biphenyls, [double (4- ammonia Base -2- carboxyls) phenyl] methane, [double (4- amino -3- carboxyls) phenyl] methane, [double (3- amino -4- carboxyls) phenyl] methane, Double [3- amino -4- carboxyl phenyls] propane of [double (3- amino -5- carboxyls) phenyl] methane, 2,2-, the double [4- amino -3- carboxylics of 2,2- Base phenyl] propane, double [3- amino -4- carboxyl phenyls] HFC-236fas of 2,2-, double [4- amino -3- carboxyl phenyls] hexafluoros third of 2,2- Alkane, 3,3'- diaminourea -4,4' dicarboxydiphenyle ther, 4,4'- diaminourea -3,3'- dicarboxydiphenyl ethers, 4,4'- diaminourea -2, 2'- dicarboxydiphenyl ethers, 3,3'- diaminourea -4,4'- dicarboxyls diphenyl sulfone, 4,4'- diaminourea -3,3'- dicarboxyl diphenyl Sulfone, 4,4'- diaminourea -2,2'- dicarboxyls diphenyl sulfone, 2,3- diaminophenols, 2,4- diaminophenols, 2,5- diaminobenzenes The diaminobenzene phenols such as phenol, 3,5- diaminophenols；3,3'- diaminourea -4,4' dihydroxy diphenyl, 4,4'- diaminourea -3,3'- The hydroxyls such as dihydroxybiphenyl, 4,4'- diaminourea -2,2'- dihydroxybiphenyls, 4,4'- diaminourea -2,2', 5,5'- tetrahydroxybiphenyl Biphenol compound class；3,3'- diaminourea -4,4'- dihydroxydiphenyls methane, 4,4'- diaminourea -3,3'- dihydroxydiphenyls The dihydroxydiphenyl methane classes such as methane, 4,4'- diaminourea -2,2'- dihydroxydiphenyl methane；Double [3- amino -4- the hydroxyls of 2,2- Base phenyl] double [hydroxy phenyl] propane classes such as propane, double [the 4- amino-3-hydroxies base] propane of 2,2-；2,2- pairs [3- amino- 4- hydroxy phenyls] double [hydroxy phenyl] HFC-236fas such as HFC-236fa, double [3- amino-4-hydroxylphenyls] HFC-236fas of 2,2- Class；3,3'- diaminourea -4,4'- dihydroxy diphenyl ethers, 4,4'- diaminourea -3,3'- dihydroxy diphenyl ethers, 4,4'- diaminourea -2, The dihydroxy diphenyl ether class such as 2'- dihydroxy diphenyl ethers；3,3'- diaminourea -4,4'- dihydroxy-diphenyl sulfones, 4,4'- diaminourea -3, The dihydroxy-diphenyl sulfone classes such as 3'- dihydroxy-diphenyl sulfones, 4,4'- diaminourea -2,2'- dihydroxy-diphenyl sulfones；3,3'- diaminos Base -4,4'- dihydroxydiphenyls thioether, 4,4'- diaminourea -3,3'- dihydroxydiphenyls thioether, 4,4'- diaminourea -2,2'- The dihydroxydiphenyl thioether class such as dihydroxydiphenyl thioether；3,3'- diaminourea -4,4'- dihydroxydiphenyls sulfoxide, 4,4'- The dihydroxydiphenyls such as diaminourea -3,3'- dihydroxydiphenyls sulfoxide, 4,4'- diaminourea -2,2'- dihydroxydiphenyl sulfoxides Sulfoxide type；Double [(hydroxy phenyl) phenyl] alkane compounds such as double [4- (the 4- amino-3-hydroxies epoxide) phenyl] propane of 2,2- Class；Double (hydroxyphenoxy) biphenol compound classes such as double (the 4- amino-3-hydroxies epoxide) biphenyl of 4,4'-；Double [4- (the 4- of 2,2- Amino-3-hydroxy epoxide) phenyl] double [(hydroxyphenoxy) phenyl] sulphones such as sulfone；4,4'- diaminourea -3,3'- dihydroxies Double [3- amino -4- carboxyl phenyls] propane of base diphenyl methane, 4,4'- diaminourea -2,2'- dihydroxydiphenyls methane, 2,2-, Double (hydroxyphenoxy) biphenol compounds such as double (the 4- amino-3-hydroxies epoxide) biphenyl of 4,4'- etc..These compounds can be independent Using or two or more is applied in combination.

The reaction of the tetracarboxylic anhydride and diamino compounds can be carried out by any means, for example, can pass through following sides Method is carried out.

Method 1：In solution obtained by tetracarboxylic dianhydride is dispersed or dissolved in organic solvent, diaminourea chemical combination is added Thing is reacted, so as to make polyamic acid solution.The ratio of the total addition level of diamino compounds now is, relative to 1 mole of tetracarboxylic dianhydride is 0.50~1.50 mole.After the reaction of tetracarboxylic dianhydride and diamino compounds terminates, by acquisition Polyamic acid solution is heated to more than 100 DEG C, less than 300 DEG C, more than 150 DEG C, less than 250 DEG C is more preferably heated to, so as to enter Row imidizate.

Method 2：Polyamic acid solution is made using with the identical method of methods described 1.Add in the polyamic acid solution Plus for carrying out the catalyst of imidizate（Preferably use pyridine, picoline, isoquinolin, trimethylamine, triethylamine, tri-n-butylamine etc. Tertiary amine）And dehydrating agent（Acetic anhydride etc.）, more than 60 DEG C, less than 180 DEG C are heated to, so as to carry out imidizate.

Method 3：Polyamic acid solution is made using with the identical method of methods described 1.The polyamic acid solution is put into More than 100 DEG C are heated to, in less than 250 DEG C of vacuum drying oven, while being heated, being dried, while taking out sucked vacuum, thus Carry out imidizate.

[（b）Spherical organic pearl]

In the present invention（b）Spherical organic pearl refers to the spherical polymer containing carbon, also includes organic pearl of ellipse.

On in the present invention（b）The average grain diameter of composition, for example, can be determined under volume reference by following methods Median particle diameter（The particle diameter corresponding with iterated integral implantation 50%）, thus using the median particle diameter measured as（b）The average grain of composition Footpath.

（Average grain diameter is determined）

Device：The equipment equal manufacture of Co., Ltd. of institute is made with Japanese hole LA-950V2

Mensuration mode：Laser diffraction/scattering formula

In the present invention（b）The average grain diameter of composition is not particularly limited, but when being 3~15 μm,（C）The softness of dielectric film Property, chemical-resistant are just superior, it is advantageous to.If average grain diameter is less than 3 μm, then sometimes can not be（C）On insulating film surface Be effectively formed bumps, thus can not obtain with（B）Good adhesion between thermosetting binding agent.If 15 μm of average grain diameter More than, then（C）The bending resistance of dielectric film is reduced sometimes.

On confirming in the present invention（C）Whether dielectric film contains（b）The method of composition, can be by any means come really Recognize.Method can be for example listed below：The one-piece type FPC of stiffening plate containing dielectric film is coated with thermosetting resin, and utilizes ion Beam is ground to the section of through-thickness, so that dielectric film exposes section, is then observed using sweep electron microscope The section of dielectric film.

（The section of dielectric film exposes）

5mm × 3mm scope is cut from the one-piece type FPC of stiffening plate with cutting knife, then using epoxy embeding resin and Cover glass, forms protection film layer and cover glass layer on the one-piece type FPC of stiffening plate cut two sides, utilize afterwards from Beamlet carries out section polishing to the section of the through-thickness of dielectric film.

（Section polishing）

Use device：The equal device with the SM-09020CP of Jeol Ltd.'s manufacture

Processing conditions：Accelerating potential 6kV

（The section observation of dielectric film）

Using scanning electron microscope, the section of the through-thickness of the dielectric film of above-mentioned acquisition is observed.

（Observation under scanning electron microscope）

Use device：The equal devices of S-3000N manufactured with High-Technologies Co., Ltd. of Hitachi

Observation condition：Accelerating potential 15kV

Detector：Back scattered electron is detected（Component patterns）

Multiplying power：1000 times

Detected in back scattered electron used（Component patterns）Under, viewing area substantially can be reflected by contrast In average atomic number difference, therefore the observed region with heavy element just relatively becomes clear（Turn white）, and with light The region of element is then darker（Black）.Therefore, the spherical organic thing of the relatively light light element such as carbon containing, hydrogen, oxygen, nitrogen is （b）Composition, is with dark（Black）The form of border circular areas is observed.

The present invention's（b）Composition is not particularly limited.For example, on the spherical organic pearl of polymethyl methacrylate system, can Enumerate product name Ganzpearl GM-0600, GM-0600W that Ganz is melted into Co., Ltd.'s manufacture.On cross-linked poly methyl propylene The sour spherical organic pearl of methyl esters system, can enumerate product name Ganzpearl GM-0801S, GM- that Ganz is melted into Co., Ltd.'s manufacture 0807S、GM-1001-S、GM-1007S、GM-1505S-S、GMX-0610、GMX-0810、GMP-0800、GMDM-050M、 GMDM-080M、GMDM-100M、GMDM-150M；The product name Techpolymer of Sekisui Plastics Co., Ltd.'s manufacture MBX-5、MBX-8、MBX-12.On the spherical organic pearl of cross-linked poly-methyl methacrylate butyl ester system, Ganz chemical conversion strain formula meetings can be enumerated Product name Ganzpearl GB-05S, GB-08S, GB-10S, GB-15S of society's manufacture, Sekisui Plastics Co., Ltd.'s system Product name Techpolymer BM30X-5, the BM30X-8 made.On the spherical organic pearl of crosslink propylene system, Ganz chemical conversions can be enumerated The product name Ganzpearl GMP-0820 of Co., Ltd.'s manufacture.On the spherical organic pearl of propylene series copolymer system, it can enumerate Ganz is melted into the product name Ganzpearl GBM-55COS of Co., Ltd.'s manufacture., can on the spherical organic pearl of cross-linked styrene system Enumerate product name Ganzpearl GS-0605, GS-1105 that Ganz is melted into Co., Ltd.'s manufacture；Ponding finished industrial strain formula Product name Techpolymer SBX-6, SBX-8 of commercial firm's manufacture.On the organic pearl of crosslinked polyacrylate system, ponding can be enumerated Product name Techpolymer ABX-8, AF10X-8, AFX-15, ARX-15 of chemical conversion product Industrial Co., Ltd manufacture.On Buddhist nun Dragon is spherical organic pearl, can enumerate the product name Ganzpearl GPA-550 that Ganz is melted into Co., Ltd.'s manufacture.On silicone-based Spherical organic pearl, can enumerate product name Ganzpearl SI-020, SI-030, SI-045 that Ganz is melted into Co., Ltd.'s manufacture. On the crosslinking spherical organic pearl of silicone-based, the product name Ganzpearl SIG-070 that Ganz is melted into Co., Ltd.'s manufacture can be enumerated. On the spherical organic pearl of crosslinking urethane system, the trade name DAIMICBEAZ of Dainichiseika Color Chem's manufacture can be enumerated UCN-8070CM Clear、UCN-8150CM Clear、UCN-5070D Clear、UCN-5150D Clear；Industrial strain on root Formula commercial firm manufacture trade name Art-pearl C-100 it is transparent, C-200 is transparent, C-300 is transparent, C-300WA, C-400 are transparent, C-400WA, C-600 are transparent, C-800 is transparent, C-800WA, P-400T, P-800T, U-600T, CF-600T, JB-400T, JB- 800T, CE-400T, CE-800T etc..They, which may be used alone or in combination, uses two or more.

Especially, if being made among above-mentioned spherical organic pearl using the organic pearl of crosslinked spherical of the intramolecular containing urethane bond For in the present invention（b）Composition, then（C）The warpage of dielectric film just can be reduced, so that the resistance to flexibility bent repeatedly can It is improved, and with（a）Caking property between composition can be improved, it is advantageous to.

Relative to（a）In the parts by weight of composition 100, the present invention（b）The allotment amount of composition is preferably 30~100 parts by weight, More preferably 40~80 parts by weight, thus can be effectively formed bumps in the insulating film surface obtained, so that with（B）Thermmohardening Adhesion between property binding agent is just superior.In addition, can also obtain by composition（b）The filling effect brought, so（C）Dielectric film Warpage can be reduced, so as to stress alleviation effects and destroy tough performance and be improved, so that the resistance to flexibility bent repeatedly It is improved.（b）If composition is less than 30 parts by weight, then with（B）Adhesion between thermosetting binding agent and it is resistance to repeatedly The flexibility of bending is poor sometimes, if more than 100 parts by weight, then the anti-flammability and application of resin composition of dielectric film When screening characteristics deteriorate sometimes, produce film foaming when coating and homogenizing it is not enough caused by bad order.

[（c）Particulate containing at least one kind of element in the group being made up of phosphorus, aluminium and magnesium]

The present invention's（c）Particulate containing at least one kind of element in the group being made up of phosphorus, aluminium and magnesium refers to as follows Particulate：At least there is 1 at least one kind of element in the group being made up of phosphorus, aluminium and magnesium in structure.

The present invention's（c）The average grain diameter of composition for example can by with it is described（b）Composition identical assay method is determined.

The present invention's（c）The average grain diameter of composition is not particularly limited, but when being 1~10 μm,（C）The softness of dielectric film Property, anti-flammability are just superior, it is advantageous to.If average grain diameter is less than 1 μm, it can not be effectively formed sometimes in insulating film surface recessed It is convex, so that with（B）Adhesion between thermosetting binding agent can be poor, if more than 10 μm of average grain diameter, then resistant to bending Property is reduced sometimes.

The present invention's（C）Whether dielectric film contains（c）Composition, can by with（C）Whether dielectric film contains（b）Composition Above-mentioned confirmation method identical method confirms.Especially, if with it is described（b）Composition identical method similarly uses thermosetting The one-piece type FPC of stiffening plate of the resin-coating containing dielectric film, and the section of through-thickness is ground using ion beam, so that Dielectric film exposes section, and the section of dielectric film is then observed using sweep electron microscope, insulation just can be clearly distinguished In film（c）Composition, it is advantageous to this method.Here, when sweep electron microscope detector with it is described（b）The feelings of composition Condition is similarly back scattered electron detection（Component patterns）When, if containing than（b）Contained element is relatively heavy in composition P elements, then can be observed dim（Burnt hair）Circular or polygonal region, if containing aluminium, magnesium elements, observable To bright（Turn white）Circular or polygonal region.

In addition, using sweep electron microscope-X-ray microanalysis instrument（SEM-EPMA, Scanning Electron Microscopy-Electron Probe X-Ray Micro Analyzer）To analyze（C）Dielectric film along thickness In the section for spending direction（c）Composition range, so as to obtain（c）The information of contained element in composition, therefore can be confirmed whether Contain phosphorus, aluminium and magnesium elements.

（Analysis under sweep electron microscope-X-ray microanalysis instrument）

Use device：The device equal manufacture of Co., Ltd. of institute is made with Japanese hole EMAX-7000

Analysis condition：Accelerating potential 15kV；Accumulated time 900 seconds

In the present invention（c）Composition is not particularly limited.For example, on the particulate containing P elements, polyphosphonic acid can be enumerated Ammonium, melamine phosphonate, phosphinic acids（phosphinic acid）Salt etc., they may be used alone or in combination using 2 kinds with On.

Among the particulate containing P elements, particularly when using phosphinates, it can make（C）Dielectric film obtains superior Anti-flammability, and from（C）The extravasation of dielectric film is less, therefore can suppress contact failure and process pollution, it is advantageous to.

The phosphinates refers to following formulas（8）

Formula（8）

Represented compound（In formula, R₅And R₆Separately represent straight-chain or the alkane of tool branch of the carbon number for 1~6 Base or aryl, M are represented to be selected from and are made up of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and K Group at least one kind of metal, t be 1~4 integer）.

As long as the phosphinates is above-mentioned structure, it is not particularly limited, for example, can enumerates：Three (diethyl time phosphines Acid) aluminium, three (first ethylphosphinic acid) aluminium, three (diphenyl phosphonic acid) aluminium, double (diethyl phosphinic acids) zinc, double (the first and second bases time phosphines Acid) zinc, double (diphenyl phosphonic acid) zinc, double (diethyl phosphinic acids) titaniums, double (first ethylphosphinic acid) titaniums, double (diphenyl time phosphines Acid) titanium etc..These compounds, which may be used alone or in combination, uses two or more.Wherein, particularly when using containing P elements and aluminium When three (diethyl phosphinic acids) aluminium of element, three (first ethylphosphinic acid) aluminium, high flame retardant can be obtained, therefore in terms of this respect, To be preferred.

In addition, on the particulate containing aluminium element, can enumerate：Hydrargillite（gibbsite）Type aluminium hydroxide, water alum clay type Aluminium hydroxide, three (diethyl phosphinic acids) aluminium, three (first ethylphosphinic acid) aluminium, three (diphenyl phosphonic acid) aluminium, they can be independent Using or two or more is applied in combination.

In addition, on the particulate containing magnesium elements, can enumerate magnesium hydroxide, magnesia, they may be used alone or in combination Use two or more.

Relative to（a）In the parts by weight of composition 100, the present invention（c）The content of composition is preferably 20~80 parts by weight, more excellent Elect 25~75 parts by weight as, the anti-flammability of the dielectric film thus obtained, electrical insulation reliability are just superior.（c）If composition is less than 20 parts by weight, then anti-flammability is poor sometimes, if more than 80 parts by weight, screening characteristics during application of resin composition can deteriorate, Produce film foaming when coating and the bad order caused by homogenizing deficiency.

[（d）Thermosetting resin]

In the present invention（d）Thermosetting resin is（C）One of inscape of resin combination of dielectric film, its be through Heat and form cross-linked structure, so as to carry out the compound of function as thermoinitiators.In the present invention, it is preferred to（C）Insulation Film be by containing（d）What the resin combination of thermosetting resin was obtained.As（d）Thermosetting resin, for example, can be used： Epoxy resin, bimaleimide resin, diallyl resistance to ground imide resin, propylene resin, metering system system resin, hydrogen The thermosetting resins such as silane hardening resin, pi-allyl hardening resin, unsaturated polyester resin；The side chain of macromolecular chain or end With pi-allyl, vinyl, alkoxysilane group, hydrosilane groups isoreactivity base chain reaction fundamental mode thermosetting high score Son etc..These thermosetting compositions, using a kind or it is appropriately combined use two or more.Wherein using use epoxy resin as （d）Composition is preferred.By containing epoxy resin ingredient, dielectric film can obtain heat resistance, and can obtain with（D）Subsidiary Wiring pattern Film between caking property, can also obtain with（B）Adhesion between thermosetting binding agent, it is advantageous to.The asphalt mixtures modified by epoxy resin Fat refers to that intramolecular contains the compound of at least one epoxy radicals.For example, on bisphenol A type epoxy resin, can enumerate：Japan Trade name jER828, jER1001, jER1002 of Epoxy Resins Co., Ltd. manufacture；Japanese ADEKA Corp.'s manufacture Trade name Adeka Resin EP-4100E, Adeka Resin EP-4300E；The commodity of Nippon Kayaku K. K's manufacture Name RE-310S, RE-410S；The trade name Epiclon840S of big Japanese ink Co., Ltd. manufacture, Epiclon850S, Epiclon1050、Epiclon7050；The trade name Epotohto YD-115 of Japanese Toto Kasei KK's manufacture, Epotohto YD-127、Epotohto YD-128.On bisphenol f type epoxy resin, it can enumerate：Japan Epoxy Trade name jER806, jER807 of Resins Co., Ltd. manufacture；The trade name Adeka of Japanese ADEKA Corp.'s manufacture Resin EP-4901E、Adeka Resin EP-4930、Adeka Resin EP-4950；Nippon Kayaku K. K's manufacture Trade name RE-303S, RE-304S, RE-403S, RE-404S；The trade name Epiclon830 of Japanese Dainippon Ink Chemicals's manufacture, Epiclon835；Trade name Epotohto YDF-170, the Epotohto YDF- of Japanese Toto Kasei KK's manufacture 175S、Epotohto YDF-2001.On bisphenol-s epoxy resin, it can enumerate：The commodity of Japanese Dainippon Ink Chemicals's manufacture Name Epiclon EXA-1514.On bisphenol-A epoxy resin, it can enumerate：Resins plants of formula meetings of Japan Epoxy Trade name jERYX8000, jERYX8034, jERYL7170 of society's manufacture；The trade name of Japanese ADEKA Corp.'s manufacture Adeka Resin EP-4080E；The trade name Epiclon EXA-7015 of Japanese Dainippon Ink Chemicals's manufacture；Japanese Dongdu chemical conversion Trade name Epotohto YD-3000, the Epotohto YD-4000D of Co., Ltd.'s manufacture., can on biphenyl type epoxy resin To enumerate：Japan Epoxy Resins Co., Ltd. manufacture trade name jERYX4000, jERYL6121H, jERYL6640, jERYL6677；Trade name NC-3000, NC-3000H of Nippon Kayaku K. K's manufacture.On phenoxy group type epoxy resin, It can enumerate：Trade name jER1256, jER4250, jER4275 of Japan Epoxy Resins Co., Ltd. manufacture.On naphthalene Type epoxy resin, can be enumerated：Trade name Epiclon HP-4032, the Epiclon HP- of Japanese Dainippon Ink Chemicals's manufacture 4700、Epiclon HP-4200；The trade name NC-7000L of Nippon Kayaku K. K's manufacture.On phenol novolak type Epoxy resin, can be enumerated：Trade name jER152, jER154 of Japan Epoxy Resins Co., Ltd. manufacture；Japanization The trade name EPPN-201-L of medicine Co., Ltd. manufacture；The trade name Epiclon N-740 of Japanese Dainippon Ink Chemicals's manufacture, Epiclon N-770；The trade name Epotohto YDPN-638 of Japanese Toto Kasei KK's manufacture.On cresol novolac Type epoxy resin, can be enumerated：Trade name EOCN-1020, EOCN-102S, EOCN- of Nippon Kayaku K. K's manufacture 103S、EOCN-104S；The trade name Epiclon N-660 of Japanese Dainippon Ink Chemicals's manufacture, Epiclon N-670, Epiclon N-680、Epiclon N-695.On tris-phenol type epoxy resin, it can enumerate：Nippon Kayaku K. K's manufacture Trade name EPPN-501H, EPPN-501HY, EPPN-502H.On dicyclopentadiene-type epoxy resin, it can enumerate：Japanization The trade name XD-1000 of medicine Co., Ltd. manufacture；The trade name EpiclonHP-7200 of Japanese Dainippon Ink Chemicals's manufacture.On Amine type epoxy resin, can be enumerated：The trade name Epotohto YH-434 of Japanese Toto Kasei KK's manufacture, Epotohto YH-434L.On pliability epoxy resin, it can enumerate：The manufacture of Japan Epoxy Resins Co., Ltd. Trade name jER871, jER872, jERYL7175, jERYL7217；The trade name Epiclon of Japanese Dainippon Ink Chemicals's manufacture EXA-4850.On urethane-modified epoxy resin, it can enumerate：The trade name Adeka of Japanese ADEKA Corp.'s manufacture Resin EPU-6、Adeka Resin EPU-73、Adeka Resin EPU-78-11., can on rubber modified epoxy resin To enumerate：Trade name Adeka Resin EPR-4023, the Adeka Resin EPR- of Japanese ADEKA Corp.'s manufacture 4026、Adeka Resin EPR-1309.On chelate modified epoxy, it can enumerate：Japanese ADEKA Corp.'s system Trade name Adeka Resin EP-49-10, Adeka Resin EP-49-20 for making etc..

Relative to（a）Composition,（b）Composition and（c）In 100 parts by weight that composition adds up to, the present invention（d）Composition is preferred For 0.5~100 parts by weight, and then preferably 1~50 parts by weight, particularly preferably 5~20 parts by weight, thus it can improve（C）Absolutely The heat resistance of velum, chemical-resistant, electrical insulation reliability, it is advantageous to.

If（d）Composition is less than the scope, then（C）The heat resistance of dielectric film, electrical insulation reliability are poor sometimes.Separately Outside, if（d）Composition is higher than the scope, then（C）Dielectric film becomes fragile sometimes and flexibility is deteriorated,（C）The warpage of dielectric film Increase sometimes.

[（e）Photoepolymerizationinitiater initiater]

In the present invention（e）Photoepolymerizationinitiater initiater is（C）One of inscape of resin combination of dielectric film, is to pass through UV（Ultraviolet, ultraviolet）Activated Deng energy, so as to trigger, promote the resin containing free-radical polymerised base to occur instead The compound answered.Therefore, containing in the present invention（e）The resin combination of Photoepolymerizationinitiater initiater is photosensitive resin composition Thing.In the present invention, preferably（C）Dielectric film be by containing（e）What the photosensitive polymer combination of Photoepolymerizationinitiater initiater was obtained.Make For in the present invention（e）Composition, for example, can enumerate：Meter Qi Le ketone, 4,4'- double (diethylamino) benzophenone, 4,4', 4''- Double (2- chlorphenyls) -4,4', the 5,5'- tetraphenyl -1,2'- diimidazoles of three (dimethylamino) triphenyl methanes, 2,2'-, benzene second Ketone, styrax, 2- benzoin methyls, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, the tertiary fourths of 2- Base anthraquinone, 1,2- benzo -9,10- anthraquinones, tectoquinone, thioxanthones, 2,4- diethyl thioxanthones, ITX, 1- Hydroxycyclohexylphenylketone, diacetyl benzil, benzil dimethyl ketal, benzil diethyl ketal, 2- (2'- furans Base ethylidene) double (trichloromethyl) s-triazine of -4,6-, 2 [2'(5''- methylfurans base) ethylidene] -4,6- are double (trichloromethyl) S-triazine, 2 (p-methoxyphenyl) -4,6- double (trichloromethyl) s-triazine, 2,6- bis- (to nitrine benzylidene) -4- methyl rings Hexanone, the nitrine chalcone of 4,4'- bis-, the nitrine stilbene -2,2'- disulfonates of two (tetra-allkylammonium) -4,4'- two, 2,2- dimethoxys - 1,2- diphenylethane -1- ketone, 1- hydroxy-cyclohexyl-phenyls -one, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] - 2- morpholinopropane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butane -1, double (2,4,6- trimethyls Benzoyl) phenyl phosphine oxide, double (2,6- Dimethoxybenzoyls) -2,4,4- trimethyl-pentyls phosphine oxides, 2,4,6- tri- Methyl benzoyl-diphenyl phosphine oxide, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, it is double (n5-2,4- cyclopentadiene - 1- yls)-bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- bases)-phenyl) titaniums, 1,2- acetyl caproyls, 1- [4- (thiophenyl) -, 2- (O- benzene Formoxyl oxime)], iodine, (4- aminomethyl phenyls) [4- (2- methyl-propyls) phenyl]-hexafluorophosphate (1-), 4- dimethylaminos Ethyl benzoate, 4- dimethylaminobenzoic acid 2- Octyl Nitrites, ethyl ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9H- Carbazole -3- bases] -, 1- (O- acetyl group oxime) etc..With appropriate from described（e）Photoepolymerizationinitiater initiater is preferred, and is preferably used in mixed way 1 More than kind.

Relative to（a）Composition,（b）Composition,（c）Composition and（d）In 100 parts by weight that composition adds up to, the present invention（e） Photoepolymerizationinitiater initiater is preferably allocated as 0.1~50 parts by weight.By using the allotment ratio, the sense of photosensitive polymer combination Photosensitiveness just can be improved, it is advantageous to.（e）If composition is less than the scope, then free-radical polymerised base during light irradiation it is anti- Should just it be not susceptible to mostly, and hardening becomes insufficient.In addition,（e）If composition is higher than the scope, then light irradiation amount Adjustment is difficult sometimes and turns into overexposure state.Therefore, in order that photo-hardening reaction efficiency is carried out well, preferably adjust In the scope.

[other compositions]

The present invention's（C）In the resin combination of dielectric film, can optionally so that using free-radical polymerised resin, coloring The additives such as agent, adhesion imparting agent, polymerization inhibitor, solvent.

Free-radical polymerised resin in the present invention, as long as it can pass through（e）The tree of Photoepolymerizationinitiater initiater formation chemical bond Fat, then do not limit.And then, free-radical polymerised base is preferably (methyl) acryloyl group or vinyl.Freedom in the present invention Base polymerizing resin is not particularly limited, for example, can enumerate：Bisphenol F EO（Ethylene Oxide, oxirane）It is modified（N= 2~50）Diacrylate, bisphenol-A EO are modified（N=2~50）Diacrylate, bisphenol S EO are modified（N=2~50）Dipropyl Olefin(e) acid ester, Bisphenol F EO are modified（N=2~50）Dimethylacrylate, bisphenol-A EO are modified（N=2~50）Dimethyl allene Acid esters, bisphenol S EO are modified（N=2~50）Dimethylacrylate, 1,6 hexanediol diacrylate, the propylene of neopentyl glycol two Acid esters, glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane trimethacrylate, pentaerythrite 3 third Olefin(e) acid ester, dipentaerythritol acrylate, tetra methylol tetraacrylate, tetraethylene glycol diacrylate, 1,6- oneself Diol dimethacrylate, neopentylglycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythrite dimethyl Acrylate, trimethylol-propane trimethacrylate, pentaerythritol acrylate trimethyl, dipentaerythritol hexamethyl third Olefin(e) acid ester, tetra methylol propane tetramethyl acrylate, tetraethylene glycol dimethylacrylate, methoxyl group diethylene glycol methyl-prop Olefin(e) acid ester, methoxy polyethylene glycol methacrylate-styrene polymer, hydrogen phthalate Beta-methyl acryloyloxyethyl ester, butanedioic acid hydrogen β- Methacryloyloxyethyl, methacrylic acid 3- chlorine-2-hydroxyls propyl ester, stearyl methacrylate, acrylic acid phenoxy group second Ester, phenoxy group diethylene glycol acrylate, phenoxy group polyethylene glycol acrylate, butanedioic acid hydrogen β-acryloyloxyethyl ester, third Olefin(e) acid lauryl, ethylene glycol dimethacrylate, dimethacrylate, triethylene glycol dimethacrylate Ester, polyethylene glycol dimethacrylate, 1,3 butylene glycol dimethylacrylate, 1,6-HD dimethylacrylate, Neopentylglycol dimethacrylate, polypropylene glycol dimethacrylate, 2- hydroxyl -1,3- dimethacryloxies third Double [4- (methacroyloxyethoxy) phenyl] propane of alkane, 2,2-, the double [4- (methacryloxies-diethoxy of 2,2- Base) phenyl] propane, double [4- (methacryloxy-polyethoxy) phenyl] propane of 2,2-, polyethyleneglycol diacrylate, Double [4- (acryloxy-diethoxy) phenyl] third of tripropylene glycol diacrylate, polypropyleneglycol diacrylate, 2,2- Alkane, 2,2- double [4- (acryloxy-polyethoxy) phenyl] propane, 2- hydroxyl -1- acryloxy -3- methacryloxypropyls Base propane, trimethylol-propane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane tetrapropylene acid Ester, methoxyl group dipropylene glycol methyl acrylate, methoxy triethylene acrylate, Nonylphenoxy polyethylene glycol acrylic acid Ester, Nonylphenoxy polypropylene glycol acrylate, 2- phthalic acid 1- acryloxy propyl ester（1- acryloyloxypropyl-2-phthalate）, the different stearyl ester of acrylic acid, polyoxyethylene alkyl ether acrylate, nonyl benzene oxygen Ethyl glycol acrylate, polypropylene glycol dimethacrylate, 1,4- butanediol dimethylacrylates, 3- methyl isophthalic acids, 5- Dimethacrylate, 1,6-HD dimethylacrylate, 1,9- nonanediols methacrylate, 2,4- diethyls Base -1,5- dimethacrylates, 1,4 cyclohexane dimethanol dimethylacrylate, DPG diacrylate Ester, Tricyclodecane Dimethanol diacrylate, 2,2- hydrogenations double [4- (acryloxy-polyethoxy) phenyl] propane, 2,2- Double [4- (acryloxy-polyethoxy) phenyl] propane, 2,4- diethyl -1,5 pentandiol diacrylate, ethoxylation Trimethylolpropane trimethacrylate, propoxylation trimethylolpropane trimethacrylate, (the ethane acrylic acid of isocyanuric acid three Ester), tetramethylol methane tetraacrylate, ethoxylation tetramethylol methane tetraacrylate, propoxylated pentaerithytol tetraacrylate, Two trimethylolpropane tetra-acrylates, dipentaerythritol polyacrylate, triallyl isocyanurate, Glycidyl methacrylate Glyceride, glycidyl allyl ether, 1,3,5- triacryls hexahydro-s-triazine, 1,3,5- benzoic acid triallyl, triolefin Propylamine, citric acid triallyl, TAP, amytal（amobarbital）, diallylamine, diallyl two Methyl-monosilane, diallyl disulphide, diallyl ether, diallyl isocyanurate, DAIP, terephthaldehyde The sub- isopropyl of diallyl phthalate, the allyloxy -2- propyl alcohol of 1,3- bis-, allyl sulfide, diallyl maleate, 4,4'- Base xenol dimethylacrylate, 4,4'- isopropylidene bisphenol diacrylates etc..Particularly preferably use diacrylate Or the EO contained by a molecule of methacrylate（Oxirane）Number of repeat unit is the resin of 2~50 scopes, Jin Eryou Select 2~40 resin.By using the resin that EO number of repeat unit is 2~50, and with following feature：Resin combination with Alkaline aqueous solution is improved for the dissolubility in the water system developer solution of representative, and developing time is reduced；Also, it is difficult in tree Residual stress in the hardened dielectric film of oil/fat composition, thus by resin combination laminated on（D）Subsidiary Wiring pattern Film on when, can suppress（D）The film of subsidiary Wiring pattern is crispaturaed.

Particularly preferably by the EO diacrylates being modified or dimethylacrylate, and with more than 3 acryloyls The acrylic resin of base or methylacryloyl is used in combination, and thus just can improve developability.For example can preferably it use：Ethyoxyl The isocyanuric acid EO modified triacrylates changed, the isocyanuric acid EO of ethoxylation are modified trimethyl acrylic ester, ethoxy The trimethylolpropane trimethacrylate of base, the trimethylolpropane trimethacrylate of ethoxylation, ethoxylation three The trimethylolpropane tris acrylic acid of hydroxymethyl-propane triacrylate, trimethylolpropane trimethacrylate, propoxylation Ester, pentaerythritol triacrylate, the tetramethylol methane tetraacrylate of ethoxylation, the pentaerythrite 4 third of ethoxylation The season penta of olefin(e) acid ester, two (trimethylolpropane) tetraacrylates, two (trimethylolpropane) tetraacrylates, propoxylation Tetra-acrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, the acryloyl-oxies of butanedioic acid 2,2,2- tri- Two (trimethylolpropane) 4 third of Methylethyl, the acryloyloxymethyl ethyl esters of phthalic acid 2,2,2- tri-, propoxylation The dipentaerythritol acrylate of olefin(e) acid ester, propoxylation, the isocyanuric acid triacrylate of ethoxylation, ε-oneself in Three ester modified (2- acrylyl oxy-ethyls）Isocyanuric acid ester, two (trimethylolpropane) tetraacrylates of caprolactone modification etc. Propylene resin.

In addition, it also may be preferable for use acrylic acid 2- hydroxyl -3- phenoxy-propyls, phthalic acid list hydroxyethyl Ester, ω-carboxyl-polycaprolactone single-acrylate, acrylic acid dimer, pentaerythritol triacrylate and pentaerythrite tetrapropylene There is hydroxyl, the compound of carbonyl in these molecular structure skeletons such as acid esters.

In addition, it is possible to use epoxide modified propylene（Metering system system）Resin, urethane-modified propylene（Methyl-prop Alkene system）The propylene of resin, polyester modification（Metering system system）Resin etc., can be used arbitrary free-radical polymerised resin.

Free-radical polymerised resin can be used a kind, but for improving the aspect of heat resistance of the dielectric film after photo-hardening, It is preferred that and using two or more.

From the viewpoint of the photonasty that can improve resin combination, relative to（a）Composition,（b）Composition,（c）Composition, （d）Composition and（e）Free-radical polymerised resin in 100 parts by weight that composition adds up to, the present invention is preferably allocated as 10~ 200 parts by weight.

If free-radical polymerised resin is less than the scope, the alkali resistance of dielectric film is reduced sometimes, and is difficult to table Reveal the contrast after exposure, development.If in addition, free-radical polymerised resin is higher than the scope, then by resin combination The viscosity for the film for being coated on base material and making solvent seasoning and obtaining will increase, so that productivity can be reduced, moreover, crosslinking Density can become too high and dielectric film may be caused to become fragile, be easily broken.By controlling in the scope, exposure can be made, shown The contrast of movie queen reaches most preferably.

As the colouring agent in the present invention, it can enumerate：Phthalocyanine based compound, Azo, carbon black, titanium oxide.Separately Outside, as adhesion imparting agent, it can enumerate：Silane coupler, three azole compounds, four azole compounds, triazine based compound. And then, as polymerization inhibitor, it can enumerate：Hydroquinones, hydroquinone monomethyl ether etc..These additives can be used alone or group Conjunction uses two or more.On the solvent in the present invention, as long as it can be used for dissolving（a）Composition and（d）The solvent of composition, then do not have It is particularly limited to, for example, can enumerates：The sulfoxide series solvent such as dimethyl sulfoxide (DMSO), diethyl sulfoxide；Monoethylene glycol dimethyl ether（1,2- bis- Ethyl Methyl Ether）, diethylene glycol dimethyl ether（Double (2- methoxy ethyls) ethers）, TRIGLYME（Double (the 2- methoxyl groups of 1,2- Ethyoxyl) ethane）, tetraethyleneglycol dimethyl ether（Double [2- (2- methoxyethoxyethyls)] ethers）, monoethylene glycol diethyl ether（1,2- Diethoxyethane）, diethylene glycol diethyl ether（Double (2- ethoxyethyl groups) ethers）, dibutyl ethylene glycol ether（Double (2- butoxy second Base) ether）Etc. symmetrical diol bisether class；Gamma-butyrolacton, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, acetic acid Butyl ester, propylene glycol methyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters（Alias：Carbitol second Acid esters, acetic acid 2- (2- Butoxyethoxies) ethyl ester）, butyl carbitol acetate, acetic acid 3- methoxybutyls, ethylene glycol Methyl ether acetate, ethylene glycol monoethylether acetate, dipropylene glycol methyl ether acetic acid esters, propylene-glycol diacetate, 1,3 butylene glycol The acetate esters such as diacetate esters；Dipropylene glycol methyl ether, tripropylene glycol methyl ether, Propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, the third two Alcohol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol positive propyl ether, propane diols phenylate, dimethyl ether, 1,3- dioxanes Ethers such as pentane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether etc..They can be single Solely use or two or more is applied in combination.

Relative to（a）Composition,（b）Composition,（c）Composition,（d）Composition and（e）100 parts by weight that composition adds up to, this hair The preferred allotment amount of solvent in bright is 10~400 parts by weight, more preferably 20~200 parts by weight, particularly preferred 40~100 weight Part.

By the way that the amount of solvent is adjusted in the scope, the viscosity of resin combination, viscosity can be adjusted to be suitable into The scope of the coating processing such as row silk-screen printing, it is advantageous to.

If solvent is less than the scope, pressed from both sides when the viscosity for having resin combination becomes very high, coating becomes difficult, applied Situation about being deteriorated with bubble, homogenization.If in addition, when solvent is higher than the scope, the viscosity for having resin combination becomes non- Often low, coating becomes the situation of difficult circuit covering property variation.

The present invention's（C）Dielectric film can be obtained in the following way：It is by each composition（a）Composition,（b）Composition,（c） Composition,（d）Composition,（e）Composition and other compositions are uniformly mixed and obtained after resin combination, and the resin combination is formed （D）On the film of subsidiary Wiring pattern, fine opening portion is optionally then formed by exposure, development, and carry out at heating Reason.On carrying out mixed uniformly method, it is not particularly limited, it is common such as using three-roll grinder, bead mill apparatus Kneading device is mixed.If in addition, the viscosity of solution is relatively low, common agitating device can be used to be mixed.Its In, particularly when using three-roll grinder, during by crushing, disperseing to be mixed,（c）Composition stool and urine is uniform, so excellent Choosing.The particle diameter of each composition in mixed resin combination, can be used the gauge of defined in JIS K5600-2-5 to carry out Determine.In addition, if using particle size distribution device, then average grain diameter, particle diameter, size distribution can be determined.

Then, the resin combination of above-mentioned acquisition can be used, dielectric film is obtained by any means.It can such as enumerate Method（1）：Resin combination is coated directly onto（D）On the film of subsidiary Wiring pattern, and it is allowed to hardening to form dielectric film；Side Method（2）：Make resin combination film forming on supporter, then attach to the film of unhardened state（D）Subsidiary Wiring pattern On film and it is allowed to hardening and forms dielectric film.It is coated directly onto by resin combination（D）Attach on the film of Wiring pattern and make Hardening come the method that forms dielectric film（1）In, resin combination is coated on first（D）On the film of subsidiary Wiring pattern, and It is dried to remove solvent.As for（D）The method being coated on the film of subsidiary Wiring pattern, can by silk-screen printing, Print roll coating, curtain, spraying, it is coated using rotary coating of circulator etc..Coated film（Preferred thickness is 5 ~100 μm）Drying, be below 120 DEG C, preferably to be carried out at 40~100 DEG C.

Then, after optionally being dried, the light shield of minus is placed on drying coating film, and it is irradiation ultraviolet radiation, visible Light, electron beam etc. activate light to be exposed.Then, using developer solution, and put by shower, leaching, impregnated or ultrasonic wave etc. Various modes are developed to unexposed portion, thus can obtain fine opening portion.Here, with the atomisation pressure of developing apparatus With flow velocity, the difference of etching solution temperature, the time untill pattern exposes is also different, therefore suitably to find out optimal dress The condition of putting is preferred.

As the developer solution, alkaline aqueous solution is preferably used.In the developer solution also can containing methanol, ethanol, normal propyl alcohol, The water-miscible organic solvents such as isopropanol, METHYLPYRROLIDONE.On the alkaline chemical combination for forming the alkaline aqueous solution Thing, for example, can enumerate：Alkali metal or alkaline-earth metal or ammonium ion, hydroxide or carbonate or bicarbonate or amines Deng.It can specifically enumerate：NaOH, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium acid carbonate, bicarbonate Potassium, ammonium hydrogen carbonate, TMAH, tetraethyl ammonium hydroxide, TPAOH, tetra isopropyl ammonium hydroxide, N- Methyl diethanolamine, N- ethyldiethanolamines, N, N- dimethylethanolamines, triethanolamine, triisopropanolamine, tri-isopropyl amine etc.. As long as the aqueous solution can be made in alkalescence, then the compound beyond these above-mentioned compounds can also be used certainly.In addition, developer solution Temperature depends on the component of resin combination, the component of alkaline-based developer, it is usually preferred to use more than 0 DEG C, less than 80 DEG C shows Shadow liquid, more preferably using more than 10 DEG C, less than 60 DEG C of developer solution.

For that through fine opening portion formed by the development step, can be rinsed and remove useless residual components Remove.As flushing liquor, water, acidic aqueous solution etc. can be enumerated.

Then, heated.By being heated, can it obtain rich in heat resistance, chemical-resistant（C）Absolutely Velum.（C）The thickness of dielectric film, can consider（D）Determined on the basis of thickness of film of subsidiary Wiring pattern etc., preferably It is 2~50 μm.In order to prevent the oxidation of conductor circuit etc. and do not make with（D）Adhesion drop between the film of subsidiary Wiring pattern It is low, preferably more than 100 DEG C, less than 250 DEG C of final heat treatment temperature now, and then preferably more than 120 DEG C, less than 200 DEG C, Particularly preferred more than 130 DEG C, less than 180 DEG C.If heat treatment temperature is too high, the oxidative degradation of conductor circuit etc. is sometimes Accelerate, and cause with（D）Adhesion between the film of subsidiary Wiring pattern is reduced.

Make resin combination film forming on supporter, then attach to the film of unhardened state（D）Subsidiary wiring diagram On the film of case and it is allowed to harden the method to form dielectric film（2）In, the equably coating resin composition first on supporter, Then heated and/or heat blow, thus a part of solvent can be removed, so as to obtain the resin combination of unhardened state Thing film.

Carry out the heating and/or heat blow to remove temperature during solvent, as long as will not cause in resin combination Contained thermosetting resin etc. crosslinks reaction because of heating.Here, used supporter is not particularly limited, Polyethylene terephthalate can be used（PET）The usual commercially available various films such as film, polyphenylene sulfide film, polyimide film.Due to PET Film has a certain degree of heat resistance, and can relatively inexpensively obtain, therefore uses PET film as support mostly in this area Body.In addition, for the composition surface between supporter and resin combination, in order to improve adhesion and fissility, it is possible to use It has passed through the supporter of surface treatment.In addition, also can on resin combination lamination diaphragm.By in the upper of resin combination Lamination diaphragm, can prevent the impurity in air or dust attachment, and can prevent that resin combination from causing bad quality because drying Change.Carry out lamination diaphragm it is preferred that being laminated on the surface of resin combination with 10 DEG C~50 DEG C of temperature.If in addition, layer Temperature during pressure processing is higher than 50 DEG C, then sometimes results in the diaphragm after the thermal expansion of diaphragm, lamination treatment and produce sometimes Raw fold is crispaturaed.In addition, diaphragm is just stripped when in use, so in keeping, preferably diaphragm and resin combination Between composition surface there is appropriate adhesion and superior fissility.

On the material of diaphragm, it is not particularly limited, for example, can enumerates：Polyethylene film（PE films）, polyvinlyethylene Alcohol film（EVA film）, polyethylene and ethylene vinyl alcohol co-polymer membrane（Hereinafter referred to as "（PE+EVA）Co-polymer membrane "）, PE films With（PE+EVA）The fitting body of co-polymer membrane, pass through simultaneously extrude（PE+EVA）Prepared by copolymer and polyethylene film（Simultaneously For PE films, another side is（PE+EVA）The diaphragm of co-polymer membrane）Deng.

Secondly, from the diaphragm for including diaphragm, resin combination, supporter, diaphragm is peeled off.Then, according to Make the film of resin combination and subsidiary Wiring pattern to mode, the film of resin combination is covered subsidiary Wiring pattern Film, and them is fitted by thermo-compression bonding.This using be thermally compressed carried out joint movement can be by hot-pressing processing, lamination at Reason（Heat lamination processing）, hot-roll lamination processing etc. carry out, be not particularly limited.Handled by heat lamination, hot-roll lamination is handled （It is designated as below " lamination treatment "）During being fitted, as long as treatment temperature is more than lower limit temperature that can be for carrying out lamination treatment （It is designated as below " the possible temperature of crimping "）.Specifically, crimp may the scope of temperature be preferably 50~150 DEG C, it is more excellent Choosing is 60~120 DEG C of scope, particularly preferably 80 DEG C~120 DEG C of scope.If treatment temperature is more than 150 DEG C, in layer During pressure processing, resin combination crosslinks reaction because of heating sometimes, causes resin combination to harden.The opposing party Face, if treatment temperature is less than 50 DEG C, the mobility of resin combination is low, it is difficult to encase pattern circuit.

Here, the resin combination of film forming is unhardened state, therefore carrying out the processing of the thermo-compression bonding such as heat lamination processing When, it has the mobility of appropriateness, the conductor circuit from the film that can preferably encase subsidiary Wiring pattern.

Handled by above-mentioned thermo-compression bonding, can obtain the lamination on the film of subsidiary Wiring pattern has resin combination and lamination There is the laminating sample of supporter.Then, if necessary in the light shield that minus is placed on the supporter of the laminating sample, irradiate ultraviolet Line, luminous ray, electron beam isoreactivity light and be exposed.Then, supporter is peeled off, using developer solution, and by drenching Bath, leaching put, impregnate or the various modes such as ultrasonic wave are developed to unexposed portion, thus can obtain fine opening portion. This, with the atomisation pressure and flow velocity of developing apparatus, the difference of etching solution temperature, time untill pattern exposes is not yet Together, therefore suitably to find out optimal device condition it is preferred.

As the developer solution, alkaline aqueous solution is preferably used.In the developer solution also can containing methanol, ethanol, normal propyl alcohol, The water-miscible organic solvents such as isopropanol, METHYLPYRROLIDONE.On the alkaline chemical combination for forming the alkaline aqueous solution Thing, for example, can enumerate：Alkali metal or alkaline-earth metal or ammonium ion, hydroxide or carbonate or bicarbonate or amines Deng.It can specifically enumerate：NaOH, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium acid carbonate, bicarbonate Potassium, ammonium hydrogen carbonate, TMAH, tetraethyl ammonium hydroxide, TPAOH, tetra isopropyl ammonium hydroxide, N- Methyl diethanolamine, N- ethyldiethanolamines, N, N- dimethylethanolamines, triethanolamine, triisopropanolamine, tri-isopropyl amine etc.. As long as it can make the aqueous solution in the compound of alkalescence, then the compound beyond these above-mentioned compounds can also be used certainly.Separately Outside, the temperature of developer solution depends on the component of resin combination, the component of alkaline-based developer, it is usually preferred to use more than 0 DEG C, 80 Developer solution below DEG C, more preferably using more than 10 DEG C, less than 60 DEG C of developer solution.

For that through fine opening portion formed by the development step, can be rinsed and remove useless residual components Remove.As flushing liquor, water, acidic aqueous solution etc. can be enumerated.

Then, heated.By being heated, can it obtain rich in heat resistance, chemical-resistant（C）Absolutely Velum.（C）The thickness of dielectric film, can consider（D）Determined on the basis of thickness of film of subsidiary Wiring pattern etc., preferably It is 2~50 μm.In order to prevent the oxidation of conductor circuit etc. and do not make with（D）Adhesion drop between the film of subsidiary Wiring pattern It is low, preferably more than 100 DEG C, less than 250 DEG C of final heat treatment temperature now, and then preferably more than 120 DEG C, less than 200 DEG C, Particularly preferred more than 130 DEG C, less than 180 DEG C.If heat treatment temperature is too high, the oxidative degradation of conductor circuit etc. is sometimes Accelerate, and cause with（D）Adhesion between the film of subsidiary Wiring pattern is reduced.

[（D）The film of subsidiary Wiring pattern]

The film of subsidiary Wiring pattern in the present invention, is had and matches somebody with somebody in the one or two sides of the basilar memebrane of 5~100 μm of thickness The film of line pattern.The preparation method of the film of subsidiary Wiring pattern in the present invention is not particularly limited, for example, can pass through such as lower section Method makes：Conductor layer is formed on basilar memebrane, flexible metal foil laminated plates are thus made, pattern erosion then is carried out to conductor layer Carve.

As long as the basilar memebrane in the present invention is the film with flexibility and with insulating properties, it is not particularly limited, for example It can enumerate：It is polypropylene, crosslinked polyethylene, polyester, polybenzimidazoles, polyimides, polyimide amide, PEI, poly- Diphenyl sulfide, liquid crystal polymer, polyether-ether-ketone etc..If not requiring heat resistance, preferred cheap polyester film, if it is desired to heat resistance, Then preferred polyimide film.

Conductor layer in the present invention is not particularly limited, for example, can enumerate：Copper or copper alloy, stainless steel or its alloy, nickel Or nickel alloy is (also including 42 alloys）, aluminum or aluminum alloy.Use has rolled copper foil, electricity more in general flexible metal foil laminated plates The Copper Foils such as Copper Foil are solved, are also preferably used in the present invention.In addition, also antirust coat or resistance to can be coated with the surface of these metal foils Thermosphere or tack coat.

The method of conductor layer, the i.e. preparation method of flexible metal foil laminated plates are formed on basilar memebrane in the present invention not to be had It is particularly limited to, for example, can enumerates：Casting method, laminating, splutting method.Casting method refers to the basilar memebrane solution coating of liquid In in conductor layer and be allowed to dry, the method for thermmohardening.Laminating refers to be formed basilar memebrane and conductor layer by being thermally compressed Method.The laminating is applied to so-called 3 layers of metal foil laminated board and so-called 2 layers of metal foil laminated board.3 layers of metal foil Laminated plates, are to intervene binding agent between basilar memebrane and conductor layer to be made.And be not involved in 2 layers of metal foil laminated board viscous Tie agent.As binding agent, epoxy resin or propylene resin etc. can be enumerated.In addition, splutting method refers to, lead on basilar memebrane Cross vacuum vapour deposition or sputtering method formation metallic film, and the method that conductor layer is formed by wet plating.Or, can also be not In the case of forming metallic film, conductor layer is formed by wet plating., can be in basilar memebrane no matter with which kind of above-mentioned method One or two sides formation conductor layer.

The pattern engraving method of conductor layer in the present invention is not particularly limited, for example, can enumerate light blockage method.Light blockage method is Refer to：Photoresist layer is formed on metal foil laminated board, is then etched, dry film is peeled off, matched somebody with somebody to be formed by exposure, development, conductor layer The method of line pattern.On photoresist layer, minus or the photoresist layer of eurymeric can be used, liquid, membranaceous etc. photoresistance is it is also possible to use Layer.Light blockage method is not particularly limited, for example, can be listed below method：By heat lamination, the formation of minus dry film type photoresistance glue is arrived On metal foil laminated board；Or, the liquid formula photoresistance glue of coating eurymeric, and be dried to be formed on metal foil laminated board.If It is minus, is then removed the part beyond exposure portion by developing, on the other hand, if eurymeric, then by developing exposure portion Remove.Dry film type photoresistance glue can be easily made thick film.On minus dry film type photoresistance glue, for example, it can enumerate：Asahi Chemical Industry's strain formula Trade name SPG-152, trade name RY-3215 of Hitachi Chemical Co., Ltd.'s manufacture of commercial firm's manufacture etc..On by aobvious The method that shadow removes photoresist layer, can suitably select, using the known chemical agent to the removing photoresistance layer that develops, for example may be used Spraying aqueous sodium carbonate（0.2~1.5% etc.）Removed etc. photoresist layer is developed.In addition, the etching on conductor layer, can be fitted Locality for example can be used potassium ferricyanide aqueous solution, ferric chloride in aqueous solution, copper chloride water-soluble from known conductor layer etching method Liquid, ammonium persulfate aqueous solution, sodium persulfate aqueous solution, aqueous hydrogen peroxide solution, hydrofluoric acid aqueous solution and combinations thereof Deng.

The one-piece type FPC of stiffening plate of the present invention, due to the contiguity between the thermosetting binding agent and dielectric film of stiffening plate Property is superior, and warpage is small, so being particularly suitable for the LCDs of small mobile terminals, sensor, for camera model institute FPC.In addition, and then can also be used for hinge bending (hinge bending), sliding bending (slide bending), electricity Cable, connector, the optical pickup for hard disk（optical pickup）FPC used etc..

<Embodiment>

Hereinafter, specifically describe the present invention by embodiment, but the present invention and be not limited to the examples restriction.

[（a）Binder polymer]

(synthesis example 1)

Into the reaction vessel for possessing mixer, thermometer, dropping funel and nitrogen ingress pipe, addition is used as polymerization The TRIGLYME of solvent（That is double (2- methoxy ethoxies) ethane of 1,2-）100.0g, is stirred under nitrogen flowing on one side, While being warming up to 80 DEG C.Into reaction vessel, 3 hours are lasted, is added dropwise and has been pre-mixed at room temperature to together from dropping funel And methacrylic acid 12.0g of the insulation under 80 DEG C of states（0.14 mole）, benzyl methacrylate 28.0g（0.16 rubs You）, butyl methacrylate 60.0g（0.42 mole）, be used as the azobis isobutyronitrile 0.5g of radical polymerization initiator.It is added dropwise After end, the temperature of reaction solution is maintained at 90 DEG C and and then has stirred 2 while be warming up to 90 DEG C by one side stirring reaction solution Hour, so as to obtain poly- (methyl) the propylene resin solution of the present invention（a-1）.Poly- (methyl) propylene resin obtained The solid component concentration of solution is 48%, and weight average molecular weight is 48,000, and acid number is 78mgKOH/g.Solid component concentration, weight are equal Molecular weight, acid number are determined by following methods.

＜ solid component concentrations ＞

It is determined according to JIS K5601-1-2.In addition, selected drying condition is 150 DEG C × 1 hour.

＜ weight average molecular weight ＞

Under the following conditions, synthesized poly- (methyl) propylene resin is determined（Equivalent to（a）Binder polymer） Weight average molecular weight.

Use device：The equal device with eastern Cao HLC-8220GPC

Chromatographic column：Eastern Cao TSK gel Super AWM-H（6.0mm I.D.×15cm）× 2

Guard column：Eastern Cao TSK guard column Super AW-H

Eluent：The H of LiBr and 20mM containing 30mM₃PO₄DMF

Flow velocity：0.6mL/min

Chromatogram column temperature：40℃

Testing conditions：RI：Polarity（+）, the response time（0.5sec）

Test article concentration：About 5mg/mL

Reference material：PEG（Polyethylene glycol）

＜ acid numbers ＞

According to JIS K5601-2-1, synthesized poly- (methyl) propylene resin is determined（Equivalent to（a）Adhesive gathers Compound）Acid number.

[synthesis example 2]

Into the reaction vessel for possessing mixer, thermometer and nitrogen ingress pipe, three second as solvent for polymerization are added Glycol dimethyl ether（That is double (2- methoxy ethoxies) ethane of 1,2-）30.00g, adds ENB diisocyanate thereto 10.31g（0.050 mole）, stir under nitrogen flowing on one side, while being heated up to 80 DEG C and being allowed to dissolve.Into the solution, last Add PCDL 50.00g within 1 hour（0.025 mole）（Asahi Kasei Corporation manufactures；Trade name PCDL T5652； Weight average molecular weight is 2000）And double (hydroxymethyl) the butyric acid 3.70g of 2,2-（0.025 mole）Dissolve into TRIGLYME Solution obtained from 30.00g.By the solution at 80 DEG C heating stirring 5 hours and be allowed to react.By anti-described in progress Should, obtaining intramolecular has the resin solution of urethane bond（a-2）.The solid component concentration of the resin solution obtained is 52%, Weight average molecular weight is 5,600, and the acid number of solid constituent is 22mgKOH/g.Solid component concentration, weight average molecular weight, acid number are logical Cross with the identical method of synthesis example 1 to determine.

[synthesis example 3]

Into the reaction vessel for possessing mixer, thermometer and nitrogen ingress pipe, three second as solvent for polymerization are added Glycol dimethyl ether（That is double (2- methoxy ethoxies) ethane of 1,2-）130.60g, adds the double adjacent benzene of 3,3', 4,4'- oxygen thereto Diformazan acid dianhydride 31.02g（0.100 mole）, double [4- (3- amino-benzene oxygens) phenyl] sulfone 34.45g（0.080 mole）, poly- (four Methylene/3- methyl tetramethyleneethers) double (PABA) the ester 24.76g of glycol（0.020 mole）, and under nitrogen flowing Stir 30 minutes, so as to obtain polyamic acid solution.

Then, the solution is heated up to 190 DEG C, reacted 2 hours.By carrying out the reaction, polyimides is obtained It is resin solution（a-3）.The solid component concentration of the resin solution obtained is 49%, and weight average molecular weight is 36,000.Solid into Point concentration, weight average molecular weight are determined using with the identical method of synthesis example 1.

（Embodiment 1~5, comparative example 1~2）

The preparation ＞ of ＜ resin combinations

Obtained into synthesis example（a）Binder polymer is added（b）Spherical organic pearl,（c）Containing selected from by phosphorus, aluminium and The particulate of at least one kind of element in the group that magnesium is constituted,（d）Thermosetting resin and other compositions, so as to make resin group Compound.The species of allotment amount and raw material of each composition raw material in resin solid content is recorded in table 1.Record each in table 1 The allotment amount and the species of raw material of resin solid content in component raw material.In addition, in table as solvent the double (2- of 1,2- Methoxy ethoxy) ethane dosage, be that the quantity of solvent in the resin solution that will be synthesized in the synthesis example is also inclusive Total solvent amount.Using defoaming device, completely disengage from the bubble in mixed solution, and implement evaluation described later.

[table 1]

Unit：Parts by weight

The ＞ of ＜ 1 are melted into the product name of the crosslinked polymethylmethacrylaparticles system organic filler of Co., Ltd.'s manufacture for Ganz, Its average grain diameter is 4 μm.

The ＞ of ＜ 2 are the product name for the spherical organic filler of crosslinking urethane system that Dainichiseika Color Chem manufactures, and it is put down Equal particle diameter is 7 μm.

The ＞ of ＜ 3 are Clariant Japan Co., Ltd. the manufactures, particulate containing phosphorus and aluminium element（Diethyl phosphinic acids Aluminium salt）Product name, its average grain diameter be 2.5 μm.

The ＞ of ＜ 4 are the product name for the glycidic amine type polyfunctional epoxy resin that Dainippon Ink Chemicals manufactures.

The ＞ of ＜ 5 are the product name for the silica dioxide granule that Aerosil Japan Co., Ltd. manufactures.

The making ＞ of the one-piece type FPC of ＜ stiffening plates evaluation test piece

Use Bake（baker）Formula applicator, in the film of the subsidiary Wiring pattern of one side（The thickness of electrolytic copper foil is 12 μm； Polyimide film is the Apical25NPI of Kaneka Co., Ltd. manufacture；Copper Foil is bonded with epoxy binding agent）Copper-clad surface On, in the way of final dry thickness turns into 25 μm, by the resin combination curtain coating of above-mentioned preparation, it is coated into 100mm × 100mm Area, and at 80 DEG C dry 20 minutes.Then, the heat hardening of 30 minutes is carried out in 150 DEG C of baking oven, so that in list The dielectric film of resin combination is formed out on the film of the subsidiary Wiring pattern in face, FPC has thus been made.Then, 185 DEG C of heat is utilized Layer of rolls press, in the polyimide film as stiffening plate（The trade name Apical125NPI of Kaneka Co., Ltd. manufacture）It is upper pre- Crimp thermosetting binding agent（The trade name Pyralux LF0100 of Dupont companies manufacture）, thus made laminate 1.Its Afterwards, by hot pressing, with 165 DEG C/90min condition, by the thermmohardening of the FPC of making insulating film surface and laminate 1 Property binding agent face is crimped each other, so that the one-piece type FPC of stiffening plate evaluation test piece has been made.

The one-piece type FPC of ＜ stiffening plates evaluation ＞

For the one-piece type FPC of stiffening plate obtained, following project is evaluated.Evaluation result is recorded in table 2 In.

（i）With the adhesion of stiffening plate

Using it is described " test film obtained in the making ＞ " columns of the one-piece type FPC of ＜ stiffening plates evaluation test piece, According to JIS K5400, evaluated using grid adhesive tape method.

"○" is represented：Implement after grid adhesive tape method, no peeling；

" △ " is represented：More than 95% grid of remaining；

"×" is represented：The remaining quantity of grid is less than 80%.

（ii）Scolding tin heat resistance

Using it is described " test film obtained in the making ＞ " columns of the one-piece type FPC of ＜ stiffening plates evaluation test piece, In the way of 260 DEG C tin soldering liquids of the one-piece type FPC of the stiffening plate reinforcement plate face with being completely dissolved is in contact, make the test film Float in the tin soldering liquid, and lifted after 10 seconds.3 operations are carried out.According to JIS K5400, by grid adhesive tape method, comment Valency thermosetting binding agent and the intermembranous adhesion strength that insulate.

"○" is represented：Implement after grid adhesive tape method, no peeling；

" △ " is represented：More than 95% grid of remaining；

"×" is represented：The remaining quantity of grid is less than 80%.

（iii）Reflow Soldering heat resistance

Using it is described " test film obtained in the making ＞ " columns of the one-piece type FPC of ＜ stiffening plates evaluation test piece, Observe the outward appearance of the test film after reflow process.The condition of Reflow Soldering is 260 DEG C：260 DEG C × 20sec of summit.

"○" is represented：Outward appearance before and after experiment is unchanged

“×”：After experiment, arbitrary lamination interface has expanded in test film.

（iv）Warpage

Using with " the method identical illustrated in the making ＞ " columns of the one-piece type FPC evaluation tests piece of ＜ stiffening plates Method, in thick 25 μm polyimide film（The trade name Apical25NPI of Kaneka Co., Ltd. manufacture）Tree is formed on surface The dielectric film of oil/fat composition, has thus made laminate 2.Then, using 185 DEG C of hot roll laminator, it is being used as stiffening plate Polyimide film（The trade name Apical125NPI of Kaneka Co., Ltd. manufacture）Upper pre-crimping thermosetting binding agent （The trade name Pyralux LF0100 of Dupont companies manufacture）, thus made laminate 1.Thereafter, by hot pressing, with 165 DEG C/90min condition, by the thermosetting binding agent face of the insulating film surface of the laminate 2 of the making and laminate 1 each other Crimping, so that the one-piece type FPC of stiffening plate evaluation test piece has been made.The test film so obtained is cut into 50mm × 50mm's Area, and by the side where stiffening plate upward in the way of, test film is positioned on somoothing board, and determine experiment bit end The depth of camber in portion.Fig. 2 is the schematic diagram of measurement site.Amount of warpage is smaller, then when meaning to be made the one-piece type FPC of stiffening plate Amount of warpage is also lower.Amount of warpage is preferably in below 5mm.

[table 2]

（Embodiment 6~8, comparative example 3）

The preparation ＞ of ＜ photosensitive polymer combinations

Obtained into synthesis example（a）Binder polymer is added（b）Spherical organic pearl,（c）Containing selected from by phosphorus, aluminium and The particulate of at least one kind of element in the group that magnesium is constituted,（d）Thermosetting resin,（e）Photoepolymerizationinitiater initiater and other into Point, so as to make photosensitive polymer combination.Recorded in table 3 resin solid content in each component raw material allotment amount, And the species of raw material.In addition, in table as solvent double (2- methoxy ethoxies) ethane of 1,2- dosage, be to be closed described Quantity of solvent in the resin solution synthesized into example also inclusive total solvent amount.Using defoaming device, make in mixed solution Bubble completely disengage from, and implement evaluation described later.

[table 3]

Unit:Parts by weight

The ＞ of ＜ 1 are melted into the product name of the crosslinked polymethylmethacrylaparticles system organic filler of Co., Ltd.'s manufacture for Ganz, Its average grain diameter is 4 μm.

The ＞ of ＜ 2 are the product name for the spherical organic filler of crosslinking urethane system that Dainichiseika Color Chem manufactures, and it is put down Equal particle diameter is 7 μm.

The ＞ of ＜ 3 are the particulate containing phosphorus and aluminium element that Clariant Japan Co., Ltd. manufactures（Diethyl phosphinic acids Aluminium salt）Product name, its average grain diameter be 2.5 μm.

The ＞ of ＜ 4 are the product name for the glycidic amine type polyfunctional epoxy resin that Dainippon Ink Chemicals manufactures.

The ＞ of ＜ 5 are the product name for the silica dioxide granule that Aerosil Japan Co., Ltd. manufactures.

The ＞ of ＜ 6 are the product name for the urethane-modified Epocryl that Nippon Kayaku K. K manufactures.

The ＞ of ＜ 7 are the product name for the Photoepolymerizationinitiater initiater that BASF Japan Co., Ltd. manufactures.

The ＞ of ＜ 8 are the product name NK Ester A-9300 of the chemical society's manufacture in Xin Zhong villages of Japan（The isocyanide urea of ethoxylation Sour triacrylate).

The making ＞ of the one-piece type FPC of ＜ stiffening plates evaluation test piece

Use Bake（baker）Formula applicator, in the film of the subsidiary Wiring pattern of one side（The thickness of electrolytic copper foil is 12 μm； Polyimide film is the Apical25NPI of Kaneka Co., Ltd. manufacture；Copper Foil is bonded with epoxy binding agent）Copper-clad surface On, in the way of final dry thickness turns into 25 μm, by the photosensitive polymer combination curtain coating of above-mentioned preparation, it is coated into 100mm × 100mm area, and dried 20 minutes at 80 DEG C.Then, irradiation accumulated exposure amount is 300mJ/cm²Ultraviolet enter Row exposure.Then, using the 1.0 weight % aqueous sodium carbonates for being heated to 30 DEG C, with 1.0kgf/mm²Ejection pressure, carry out The spray development of 90 seconds.After development, fully cleaned using pure water, the heating of 30 minutes has then been carried out in 150 DEG C of baking oven Hardening, so as to form out the dielectric film of photosensitive polymer combination on the film of the subsidiary Wiring pattern of one side, is thus made FPC.Then, using 185 DEG C of hot roll laminator, in the polyimide film as stiffening plate（The manufacture of Kaneka Co., Ltd. Trade name Apical125NPI）Upper pre-crimping thermosetting binding agent（The trade name Pyralux of Dupont companies manufacture LF0100）, thus made laminate 1.Thereafter, by hot pressing, with 165 DEG C/90min condition, by the FPC's of the making Insulating film surface is crimped each other with the thermosetting binding agent face of laminate 1, so that the one-piece type FPC of stiffening plate evaluation has been made Test film.

The one-piece type FPC of ＜ stiffening plates evaluation ＞

For the one-piece type FPC of stiffening plate obtained, following project is evaluated.Evaluation result is recorded in table 4 In.

（i）With the adhesion of stiffening plate

Using it is described " test film obtained in the making ＞ " columns of the one-piece type FPC of ＜ stiffening plates evaluation test piece, According to JIS K5400, evaluated using grid adhesive tape method.

"○" is represented：Implement after grid adhesive tape method, no peeling；

" △ " is represented：More than 95% grid of remaining；

"×" is represented：The remaining quantity of grid is less than 80%.

（ii）Scolding tin heat resistance

Using it is described " test film obtained in the making ＞ " columns of the one-piece type FPC of ＜ stiffening plates evaluation test piece, In the way of 260 DEG C tin soldering liquids of the one-piece type FPC of the stiffening plate reinforcement plate face with being completely dissolved is in contact, make the test film Float in the tin soldering liquid, and lifted after 10 seconds.3 operations are carried out.According to JIS K5400, by grid adhesive tape method, comment Valency thermosetting binding agent and the intermembranous adhesion strength that insulate.

"○" is represented：Implement after grid adhesive tape method, no peeling；

" △ " is represented：More than 95% grid of remaining；

"×" is represented：The remaining quantity of grid is less than 80%.

（iii）Reflow Soldering heat resistance

Using it is described " test film obtained in the making ＞ " columns of the one-piece type FPC of ＜ stiffening plates evaluation test piece, Observe the outward appearance of the test film after reflow process.The condition of Reflow Soldering is 260 DEG C：260 DEG C × 20sec of summit.

"○" is represented：Outward appearance before and after experiment is unchanged

“×”：After experiment, arbitrary lamination interface has expanded in test film.

（iv）Warpage

Using with " the method identical illustrated in the making ＞ " columns of the one-piece type FPC evaluation tests piece of ＜ stiffening plates Method, in thick 25 μm polyimide film（The trade name Apical25NPI of Kaneka Co., Ltd. manufacture）Sense is formed on surface The dielectric film of photosensitive resin composition, has thus made laminate 2.Then, using 185 DEG C of hot roll laminator, it is being used as benefit The polyimide film of strong plate（The trade name Apical125NPI of Kaneka Co., Ltd. manufacture）Upper pre-crimping thermosetting is bonded Agent（The trade name Pyralux LF0100 of Dupont companies manufacture）, thus made laminate 1.Thereafter, by hot pressing, with 165 DEG C/90min condition, by the thermosetting binding agent face of the insulating film surface of the laminate 2 of the making and laminate 1 Crimp each other, so that the one-piece type FPC of stiffening plate evaluation test piece has been made.By the test film so obtained be cut into 50mm × 50mm area, and by the side where stiffening plate upward in the way of, test film is positioned on somoothing board, and determine examination Test the depth of camber of piece end.Fig. 2 is the schematic diagram of measurement site.Amount of warpage is smaller, then means stiffening plate is made one-piece type Amount of warpage during FPC is also lower.Amount of warpage is preferably in below 5mm.

[table 4]

The present invention is not limited to each scheme discussed above, and various changes can be carried out in the scope shown in claim More, the technical scheme each disclosed in appropriately combined different embodiments and embodiment and the embodiment and embodiment that obtain In the technical scope of the present invention.

[industrial utilizability]

The present invention may be used in the field of flexible printing substrate（Such as field of mobile phone, video camera, notebook computer）.

Claims (4)

1. a kind of one-piece type flexible printing substrate of stiffening plate, it is characterised in that：It, which is sequentially connected, contacts to earth comprising stiffening plate, thermmohardening Property binding agent, dielectric film, the film of subsidiary Wiring pattern, wherein,

The dielectric film at least contains binder polymer and spherical organic pearl.

2. the one-piece type flexible printing substrate of stiffening plate according to claim 1, it is characterised in that：

The dielectric film also contains：Particulate containing at least one kind of element in the group being made up of phosphorus, aluminium and magnesium.

3. the one-piece type flexible printing substrate of stiffening plate according to claim 1 or 2, it is characterised in that：

The dielectric film is obtained by the resin combination containing thermosetting resin.

4. the one-piece type flexible printing substrate of stiffening plate according to claim 1 or 2, it is characterised in that：

The dielectric film is obtained by the photosensitive polymer combination containing Photoepolymerizationinitiater initiater.